CN113533401A - Method for measuring chemical composition in chromium ore by using X-ray fluorescence spectrum - Google Patents
Method for measuring chemical composition in chromium ore by using X-ray fluorescence spectrum Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000011651 chromium Substances 0.000 title claims abstract description 46
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 title claims abstract description 34
- 238000004876 x-ray fluorescence Methods 0.000 title abstract description 12
- 238000001228 spectrum Methods 0.000 title abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000004907 flux Effects 0.000 claims description 31
- 238000004846 x-ray emission Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 4
- -1 alkali metal salt Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 32
- 239000012895 dilution Substances 0.000 description 12
- 238000010790 dilution Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005464 sample preparation method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910013184 LiBO Inorganic materials 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 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 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OYLGLPVAKCEIKU-UHFFFAOYSA-N diazanium;sulfonato sulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OS([O-])(=O)=O OYLGLPVAKCEIKU-UHFFFAOYSA-N 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001304 sample melting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
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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 provides a method for measuring chemical compositions in chromium ore by utilizing X-ray fluorescence spectrum. The method combines a melting method and a tabletting method, only a chromium ore sample and a fusing agent are added into a crucible, the mixture is heated and melted, then cooled and crushed, and then the chromium ore sample is prepared by tabletting, and then the chemical composition in the sample is determined by utilizing X-ray fluorescence spectrum. Compared with the prior art, the method has the advantages of low cost, simplicity, easy implementation, high detection accuracy and good detection limit for low-content elements.
Description
Technical Field
The invention belongs to the technical field of chemical composition determination in minerals. In particular to a method for measuring chemical compositions in chromium ore by utilizing X-ray fluorescence spectrum.
Background
Chromium and its compounds have a wide range of applications in industry, such as for stainless steel, corrosion resistant coatings, refractory materials, etc. The main source of chromium is chromium-containing minerals (collectively referred to herein as chromium ore), which may be generally represented by the formula (Fe, Mg) O (Cr, Fe, Al)2O3) It is indicated that the chemical composition of different kinds of chromium ores varies, for example chromite is a complex mineral composed mainly of iron (Fe), magnesium (Mg) and chromium (Cr) oxides and some other chemical elements, often expressed in chemical formula (Fe, Mg) Cr2O4. For the same kind of chromium ore, when the producing area is notMeanwhile, the content of the main chemical elements may be different, and the composition and content of other added elements may also be different. For example, not only the contents of Fe, Mg and Cr may be different in chromite ores of different origins, but also the compositions of other elements are greatly different. The difference of the chemical composition not only affects the mining value and the transaction price of the chromium ore, but also affects the application field and the smelting technical route, so that the accurate determination of the chemical composition of the chromium ore has important significance for related fields of mining, smelting, application and the like of the chromium ore.
The traditional method for analyzing the chemical composition of chromium ore is a chemical method, which needs more chemical reagents, has complex operation and low detection efficiency, and has limited content range of detectable chemical components. For example, ASTM E342-11 Standard uses potassium permanganate titration to determine Cr in chromium ores2O3At content, sodium peroxide (Na) is used2O2) Sulfuric acid (H)2SO4) Nitric acid (HNO)3) Phosphoric acid (H)3PO4) Silver nitrate (AgNO)3) Potassium permanganate (KMnO)4) Ammonium pyrosulfate ((NH)4)2S2O8) Sodium chloride (NaCl), ammonium ferrous sulfate hexahydrate (FeSO)4(NH4)2SO4.6H2O), titration indicator, etc., and the operation is complicated, the detection efficiency is low, and the method is only suitable for Cr2O3The content range is 25-60% of chrome ore.
An X-ray fluorescence spectroscopy (XRF) method is a rapid chemical composition analysis method capable of simultaneously measuring multiple elements, and is widely applied to the fields of mines, metallurgy, geology, chemical industry, steel and the like. XRF is increasingly used in the chemical composition determination of chromium ore.
In XRF measurement of chemical composition in minerals, one key factor affecting accuracy and measurement efficiency is the sample preparation method. The powder tabletting method is a rapid sample preparation method, but the particle size and mineral effect have large influence on the accuracy of a detection result, so the powder tabletting method is less adopted in the precise quantitative analysis of minerals. The melting method is another sample preparation method which is commonly used at present, and is to mix a sample to be detected with a solvent, an oxidant, a release agent and the like, pre-oxidize and melt the mixture, and prepare a transparent glass sheet. The influence of granularity and mineral effect on the detection result can be greatly reduced or even eliminated by preparing a sample by a melting method, but the following problems exist:
(1) at present, precious metal alloy crucibles and molds such as platinum (Pt), gold (Au) and the like are needed to be used when the glass fuse piece is prepared by a melting method, for example, the crucibles and molds which are commonly used have the mass percentage of 95% Pt and 5% Au, so the cost is very high, and the crucibles need to be frequently refined and processed again due to the corrosion of the melt, so the preparation and use cost of the sample is further improved, and the detection cost is integrally improved.
(2) The operation is complicated by adopting mixed flux, oxidant, release agent and the like;
(3) at present, lithium tetraborate (Li) is generally used in order to obtain high quality molten glass sheets2B4O7) And lithium metaborate (LiBO)2) As a mixed flux, melts at temperatures above 1100 ℃ and is not conducive to the detection of components that are susceptible to volatilization at high temperatures;
(4) in the fusion process, the selection of the fluxing agent and dilution ratio is important in order to obtain high quality molten glass sheet. Considering Cr2O3The ratio of the concentration of the sample to the concentration of the flux must be low (this ratio is called dilution ratio, i.e. dilution ratio is the concentration of the sample: concentration of the flux), and lithium tetraborate (Li) is used2B4O7) And lithium metaborate (LiBO)2) The flux mixture generally has a dilution ratio of 1: (20-50), low dilution ratio results in poor detection limit and reduced sensitivity.
Thus, there are a number of factors that need to be taken into account when using XRF to determine the chemical composition of chromium ore. The following are problems associated with prior art methods for determining chemical constituents in chromium ore using XRF.
The China entry and exit inspection and quarantine standard SN/T1118-. Sodium hexametaphosphate and lithium metaborate are used as flux, in an alloy crucible of platinum (Pt) and gold (Au), the flux is melted by a muffle furnace at 1150 ℃, and lithium bromide is added as a release agent. In the method, sodium hexametaphosphate is used as a flux, so that phosphorus in the ore cannot be measured, and the content of the phosphorus is expected to be known in a smelting process. In addition, the use of a noble metal crucible leads to an increase in use cost. And the prepared sample wafer is easy to crack and absorb moisture, so that the measurement is influenced.
Xuzhen et Al published article "research on method of measuring chromium ore melting by X-ray fluorescence spectrometry" ("Metallurgical analysis", 35 (7): 27-31, 2015), and found out that a glass sheet is prepared by melting lithium metaborate and sodium nitrate (mass ratio 3: 1) at 1150 ℃ and Cr, Si, Fe, P and Al in chromium ore are measured by XRF method. In addition to the increase in the use cost due to the use of a noble metal crucible, the authors of the present invention have pointed out that "solubility in a high-temperature molten state is difficult to measure and the solubility curve obtained by visual observation is not accurate", and therefore "further research is required".
In the paper published by the Bomegger et al, "X-ray fluorescence spectrometry for powder tabletting sample preparation" for measuring 6 oxides in chrome ore "(" physicochemical examination-chemistry division, 53: 978-.
In the paper published by Zengjiangnun et al, "analyzing chromite by melting and sampling X-ray fluorescence spectrometry with lower dilution ratio" ("rock and ore test", 32 (6): 915-: flux 1: 20 "low dilution ratio" melt samples, even with samples reported in the literature: flux 1: 50 to achieve melt sampling. However, when the low dilution ratio is adopted, the sample weighing amount is small, so that the detection limit is deteriorated, and the measurement of low-content elements is not facilitated.
Patent application CN110082379A discloses a method for measuring 14 major and minor components in chromium ore by melting sample preparation-X-ray fluorescence spectroscopy, wherein lithium tetraborate (Li) is adopted2B4O7) And lithium metaborate (LiBO)2) Flux was mixed as sample: flux 1: a low dilution ratio of 20 was metered into the oxidation-demould mix solution (NaNO)3-LiBr) melting and sample preparation, and then measuring 14 main and secondary components in the chromium ore by XRF. However, the low dilution ratio deteriorates the detection limit and lowers the sensitivity, and the use of a platinum-gold alloy crucible is required for melting, which leads to a high detection cost.
Disclosure of Invention
In view of the above technical situation, the present invention aims to provide a method for determining chemical composition in chromium ore by using X-ray fluorescence spectroscopy (XRF), which is low in cost, simple and easy to implement, and has high detection accuracy.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows: a method for determining chemical composition in chromium ore by X-ray fluorescence spectroscopy comprises a process of preparing a sample, and a process of determining chemical composition in the sample by X-ray fluorescence spectroscopy; the method is characterized in that: the procedure for preparing the samples was as follows:
s1: collecting a sample in chromium ore, grinding, drying and cooling;
s2: adding a sample and a fusing agent into a crucible, heating, melting and uniformly mixing to obtain a mixture;
s3: the mixture was cooled and pulverized into powder, and then tabletted to prepare a sample.
In step S1, the grinding method is not limited, and the grinding may be performed by a mechanical method, by a manual method using an agate mortar, or by an automatic sample grinder. Preferably, the particle size of the sample after grinding is less than 100 μm. More preferably, the sample is dried after polishing.
In step S2, the heating temperature is low to prevent volatile components in the sample from volatilizing at high temperature and being undetectable, for example, the heating temperature is preferably lower than 1000 ℃, more preferably lower than 900 ℃, and most preferably in the range of 700 ℃ to 900 ℃.
In step S2, the flux is melted at a heating temperature, and the flux is not limited. Preferably, the melting point of the flux is less than 1000 ℃, more preferably less than 900 ℃, and most preferably the melting point is in the range of 700 ℃EIn the range of 900 ℃. For example, an alkali metal salt of pyrosulfuric acid, of formula M, may be selected as the flux2S2O7M is one or two of alkali metals Na, K and the like.
In the step S2, the crucible is not limited, and a noble metal material, such as a quartz crucible, may not be used because a glass fuse needs not to be prepared, so that the cost can be greatly reduced.
In step S2, the crucible is preferably shaken during the heating process to promote the mixing of the sample and the solvent.
In the step S2, the melting time is preferably 15 to 60 min.
In step S2, the flux is preferably an analytically pure or higher purity reagent, wherein the impurity concentration should not affect the detection.
In step S2, the flux is preferably ground and dried before use, and contains no moisture.
In the step S2, a muffle furnace is preferably used for heating, and further preferably, the maximum temperature of the muffle furnace can reach 1000 ℃, and the temperature control precision is better than +/-5 ℃.
In step S3, the mixture is cooled and then pulverized, and the method of pulverization is not limited, but is preferably grinding. Preferably, the powder is pulverized into a powder having a particle size of 48 to 100. mu.m.
In step S3, tabletting is to press the powdered mixture into tablets under pressure. The method of tableting is not limited and can be done on a tableting machine, etc. Further preferably, the tablet press has a pressure of 20kN to 40 kN.
In the process of measuring the chemical composition in the sample by using the X-ray fluorescence spectrum, preferably, the standard sample used for the quantitative measurement of the X-ray fluorescence spectrum adopts the same sample preparation method and sample preparation conditions as those of the unknown sample. The standard sample can be a certified standard substance or a similar standard substance, and the element content can be adjusted by adding a spectrally pure oxide.
In the process of measuring the chemical composition in the sample by using the X-ray fluorescence spectrum, preferably, after the intensity is measured by using the X-ray fluorescence spectrum, data processing is performed by using software with a matrix correction function to obtain the concentration of each detection component in the unknown sample.
Compared with the prior art, the method combines a melting method and a tabletting method, only the chromium ore sample and the fusing agent are added into the crucible, the mixture is heated and melted, then cooled and crushed, and then the chromium ore sample is prepared by tabletting, and then the chemical composition in the sample is determined by utilizing the X-ray fluorescence spectrum, so that the method has the following beneficial effects:
(1) according to the invention, the influence of mineral effect can be basically overcome through melting, the XRF analysis can be ensured to obtain an accurate detection result, the accuracy of the detection result is obviously superior to that of a tabletting method and is equivalent to that of a common melting method;
(2) in the invention, because glass sheets do not need to be prepared in the heating and melting process, on one hand, an oxidant, a release agent and the like do not need to be added, the cost is low, the operation is simple and convenient, and on the other hand, a low dilution ratio is not needed, so that the detection limit of low-content elements can be ensured, for example, the dilution ratio can be selected to be 1 (4-15), and more preferably 1 (4-8).
(3) In the invention, the crucible does not need to be made of noble metal materials, for example, a transparent quartz crucible can be used, so that the equipment cost and the use requirement are greatly reduced, and the detection cost is reduced;
(4) in the present invention, the flux is selected widely, and for example, alkali metal salt of pyrosulfuric acid, which has a chemical formula of M, can be selected as the flux2S2O7M is one or two of alkali metals Na and K; the flux may be selected according to the composition of the chromium ore sample and the demand for detection, and for example, if potassium (K) element is required to be detected during detection, K element is not included in the flux, and if sodium (Na) element is required to be detected during detection, Na element and the like are not included in the flux.
Therefore, the method has the advantages of simple and easy sample preparation, low cost, high element detection limit, good application prospect in chromium ore detection, and expanded application to chemical composition analysis of other minerals difficult to melt by a conventional sample melting method similar to chromium ore.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
Example 1:
in this embodiment, the method for measuring the chemical composition of chromium ore includes a process of preparing a sample, and a process of measuring the chemical composition of the sample using X-ray fluorescence spectroscopy.
The procedure for preparing the samples was as follows:
(1) samples were collected from chromium ore, mechanically ground to a particle size of less than 150 mesh (100 μm), dried at 105 ℃ for 2h, and cooled in a desiccator.
(2) The flux is Na2S2O7Or K2S2O7One of the two methods can be selected according to the composition of the chromium ore sample to be detected and the detection requirement. If potassium (K) element needs to be detected in the detection, K is not used2S2O7Used as a fusing agent. If the detection of sodium (Na) element is required, Na is not used2S2O7Used as a fusing agent. The flux is a reagent with analytical purity or higher purity, wherein the content of impurities should not influence the detection result. The flux is ground and dried before use, and contains no moisture.
Accurately weighing 0.5g of the sample and 6.000g of the flux K with an electronic balance having an accuracy of 0.1mg2S2O7The mixture was mixed in a vitreous silica crucible having a capacity of 30ml, and the crucible was covered with a crucible cover.
(3) Heating the quartz crucible in a muffle furnace to 1000 deg.C with temperature control precision better than + -5 deg.C, maintaining the temperature for 15min after the flux is completely melted, and shaking the crucible for 2 times to make the flux and the sample uniform; then the temperature is raised to 750 ℃, the melting is continued for about 30min, and the crucible is shaken for 3 times in the process.
(4) Taking out the crucible, naturally cooling at room temperature, and grinding into powder with the particle size of about 100 mu m in an agate mortar; the powder was then loaded into a die, which size was determined according to the XRF spectrometer used, and the sample was pressed on a tablet press at 40kN and held for 30 s.
The chromium ore standard samples GBW07201 and GBW07202 are used as samples to be tested, the samples are prepared by the sample preparation method, and the samples are measured by the common X-ray fluorescence spectrum quantitative analysis method.
The chromite (or similar) standard substances GBW07818, GBW07819, GBW07820, GBW07821, GBW07280 and GBW07292 are used as standard samples, and after the samples are prepared by the same method, the measurement conditions are measured on a Panalytical Axios wavelength dispersive X-ray fluorescence spectrometer and are shown in Table 1.
TABLE 1 measurement conditions (proportional gas flow detector FL, scintillation detector DU + closed proportional detector DU)
After the spectral line intensity of the standard sample is obtained through measurement, quantitative analysis software carried by instrument equipment is used for making a correction curve of each element, and a theoretical influence coefficient is used for correcting the matrix. GBW07201 and GBW07202 were then measured as unknown samples, and the standard values, the measurements (XRF measurements), the Relative Standard Deviations (RSD) of the 6 measurements and the method detection limits are shown in Table 2.
From the data in table 2, it can be found that when the sample preparation method of the present invention is used for XRF detection of chromium ore samples, the detection result accuracy is obviously better than that of the tabletting method in the literature and is equivalent to that of the general melting method, but the detection limit is totally better than that of the melting method reported in the general literature.
TABLE 2 measurement of two standard samples GBW07201 and GBW07202 as unknown samples
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for determining chemical composition in chromium ore by X-ray fluorescence spectroscopy comprises a process of preparing a sample, and a process of determining chemical composition in the sample by X-ray fluorescence spectroscopy; the method is characterized in that:
the procedure for preparing the samples was as follows:
s1: collecting a sample in chromium ore, grinding, drying and cooling;
s2: adding a sample and a fusing agent into a crucible, heating, melting and uniformly mixing to obtain a mixture;
s3: the mixture was cooled and pulverized into powder, and then tabletted to prepare a sample.
2. The method of claim 1, further comprising: in the step S1, the grain diameter of the ground sample is less than 100 μm;
preferably, the sample is dried after polishing.
3. The method of claim 1, further comprising: in step S2, the heating temperature is lower than 1000 ℃, more preferably lower than 900 ℃, and most preferably in the range of 700 ℃ to 900 ℃.
4. The method of claim 1, further comprising: in step S2, the melting point of the flux is lower than 1000 ℃, more preferably lower than 900 ℃, and most preferably the melting point is in the range of 700 ℃ to 900 ℃;
preferably, the flux is ground and dried before use.
5. The method of claim 4, wherein: the flux is an alkali metal salt of pyrosulfuric acid;
preferably, the flux is Na2S2O7、K2S2O7One or two of them.
6. The method of claim 1, further comprising: in the step S2, the crucible is a quartz crucible.
7. The method of claim 1, further comprising: in step S2, the crucible is shaken during the heating process.
8. The method of claim 1, further comprising: in the step S2, the melting time is 15 to 60 min.
9. The method of claim 1, further comprising: in step S3, the mixture is cooled and then ground, and the particle size of the powder is 48 to 100 μm.
10. The method of claim 1, further comprising: in the step S3, tabletting is completed on a tablet press;
preferably, the tablet press has a pressure of 20kN to 40 kN.
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| CN110082379A (en) * | 2019-04-09 | 2019-08-02 | 湛江出入境检验检疫局检验检疫技术中心 | The method that MTG YBCO bulk-X-ray fluorescence spectra surveys 14 kinds of major and minor components in chrome ore |
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