CN105699409B - The method that x-ray fluorescence glass flux sheet method measures barium sulfate content in barite - Google Patents
The method that x-ray fluorescence glass flux sheet method measures barium sulfate content in barite Download PDFInfo
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- CN105699409B CN105699409B CN201610104932.XA CN201610104932A CN105699409B CN 105699409 B CN105699409 B CN 105699409B CN 201610104932 A CN201610104932 A CN 201610104932A CN 105699409 B CN105699409 B CN 105699409B
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- barium
- barite
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- barium sulfate
- aluminium
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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
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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
Abstract
The present invention relates to a kind of methods that x-ray fluorescence glass flux sheet method measures barium sulfate content in barite, after removing the barium carbonate in sample with acidleach, x-ray fluorescence glass flux sheet method measures the barium sulfate in barite, barium sulfate standard series is made with barite national standard substance and labor standard, the assay method of research is fast and convenient, detection limit is low, and test quality meets《Geological and mineral laboratory test quality control procedure》The requirement of (DZ/T 0130-2006).
Description
Technical field
The present invention relates to barium sulfite determination fields, and in particular to a kind of x-ray fluorescence glass flux sheet method measures in barite
The method of barium sulfate content.
Background technology
The exploitation and research of nonmetallic minerals are all attached great importance in countries in the world at present, constantly to expand opening for nonmetallic minerals
It sends out type and utilizes field.Barite be widely used in the heavy weight additive of petroleum and natural gas drilling mud, production baric industrial chemicals,
The shielding in atomic-energy factory and X-ray laboratory, the contrast agent etc. of medical industry digestive system.Barite belongs to non-renewable money
Source with the development of industry increasingly requires quick and precisely the analysis of barite.Barium sulfate is the main of evaluation barite quality
Index, the assay method of barium sulfate is explored by years of researches in barite, never in Simplified analysis formality and raising
It makes a breakthrough simultaneously in terms of analysis quality, existing analysis method flow is complicated, and disturbing factor is more, analytical cycle is long,
Testing cost is high, has been unable to meet growing production requirement.
Temporarily without national standard, the analysis method used at present mainly has the assay method of barium sulfate in barite：Barium chromate
The detection limit of volumetric method and gravimetric method, two methods is higher, and measurement range is>3% barium sulfate.Barium chromate volumetric method point
Analysis condition is harsh, not easy to control, it is desirable that analysis personnel have higher operative skill and skillfully grasped to analysis method, are answered in production
With less；Barium sulfategravimetry although flow is complicated, energy consumption is huge, stablize relatively by method application, thus be current application most
More methods, strontium and lead precipitate simultaneously with barium in this method analytic process, need to the sample result containing strontium, lead otherwise into
In addition row correction, need to increase an analysis process.
Invention content
The purpose of the present invention is to provide the sides that a kind of x-ray fluorescence glass flux sheet method measures barium sulfate content in barite
Method, after the barium carbonate in sample is removed with acidleach, x-ray fluorescence glass flux sheet method measures the barium sulfate in barite, with barite
National standard substance and labor standard make barium sulfate standard series, and the assay method of research is fast and convenient, and detection limit is low, and survey
Quality is tried to meet《Geological and mineral laboratory test quality control procedure》The requirement of (DZ/T 0130-2006).
The technical solution adopted by the present invention to solve the technical problems is：X-ray fluorescence glass flux sheet method measures barite
The method of middle barium sulfate content, includes the following steps：
A. sample pre-treatment：The accurate sample 0.2000g weighed in 105 DEG C of dry 2h, is placed in 50mL beakers, adds
The hydrochloric acid of 10mL10wt%, the nitric acid of 4mL10wt%, cap upper surface ware are heated in heating slightly boiling 30min on low temperature electric hot plate
It is 10mL to add water management volume at any time in the process, removes, is rinsed with water surface plate and wall of cup, is cooled to room temperature, use slow filter paper
All undissolved samples are moved on filter paper, are washed to no chlorion by filtering, and precipitation is placed in 50mL porcelain together with filter paper
In crucible, heat up ashing is placed in high temperature furnace after low temperature drying, in 700 DEG C of calcination 30min, taking-up is cooled to room temperature, is transferred to
Weighing disk weigh calcination amount of substance, 0.2000g is added with high purity aluminium oxide, is placed in former crucible, weigh 6.0000g flux,
0.5g ammonium nitrate stirs evenly in crucible, is transferred in platinum-gold crucible, adds saturation lithium-bromide solution 0.4mL, in high frequency fusion machine
Upper 650 DEG C of pre-oxidation 3min, 1075 DEG C of melting 2min add ammonium iodide 20mg, shake melting 4.5min, then add ammonium iodide 20mg,
It pours into warmed-up platinum-gold alloy mold after shaking melting 1.5min, is poured out after being cooled to room temperature；
B. assay：It will be cooled to that room temperature, treated, and sample is placed in XRF spectrometer sample introduction exchangers measures：
Standard series：Standard curve, barite country mark are made with national standard substance and the calibration sample manually prepared
Quasi- substance：GBW07811~GBW07817, rock national standard substance GBW07111, GBW07132, high-purity BaSO4, Yi Jiren
The calibration sample that work is prepared does standard series；
Instrument operating condition：According to the property of barium element, to the analysis condition of main preservation element and barium in barite into
Selection is gone：
Current/voltage：Barium and light element select low-voltage, high current；
Collimator：Barium and light element select thick collimator；
Optical filter：Bromine, strontium, zinc select Al optical filters, reduce scattering background, eliminate miscellaneous line interference；Barium and other elements choosing
It selects free of light filter；
Peak angle：It is scanned with barite samples prepared by fuse piece method, the peak position obtained according to scanning determines peak value
Angle；
Background dot：The background dot selection of barium, strontium, bromine, zinc, sulphur, silicon is in long wave side；Iron, titanium, calcium, potassium, aluminium background click
It selects in shortwave side；Respectively there are one background dots in the long shortwave both sides of spectral peak for magnesium, sodium；
PHD：To filter out influence of the interference spectral line to barium element, makees PHD distribution occasion inspections, determine PHD upper lower limit values；
Time of measuring：Time of measuring is determined according to the accuracy requirement of the property of element and measurement；
C. testing result：Detection is limited to 0.0087%, and measurement is limited to 0.18%.
Specifically, in the step a flux by 67wt% Li2B4O7With the LiBO of 33wt%2Composition.
The invention has the advantages that：1, dilute hydrochloric acid and dust technology mixed processing sample are used for the first time, make barite
In barium carbonate and non-ferrous metal preferably removed, eliminate interference of the previous barium carbonate to barium sulfite determination；There is coloured gold
Non-ferrous metal generates corrosion to platinum yellow crucible during the removal of category eliminates molten sample.2, the high pure zirconia of additive is used for the first time
Aluminium, the Matrix effects that sample itself generates reduce.3, the calibration sample manually prepared with high-purity sulphuric acid barium and national standard substance
Standard series is done, the accuracy of test method is improved and meets the analysis requirement of each content range of sample；4, detection is limited to
0.18%, analytical cycle is the one third of current methods, and analysis cost is the 30% of current methods, realizes low cost and height
Effect test, test quality meet《Geological and mineral laboratory test quality control procedure》The requirement of (DZ/T 0130-2006).
Specific implementation mode
The following is specific embodiments of the present invention, is described further to technical scheme of the present invention, but the present invention
Protection domain is not limited to these examples.It is every to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection domain within.
The method that x-ray fluorescence glass flux sheet method measures barium sulfate content in barite, includes the following steps：
A. sample pre-treatment：The accurate sample 0.2000g weighed in 105 DEG C of dry 2h, is placed in 50mL beakers, adds
The hydrochloric acid of 10mL10wt%, the nitric acid of 4mL10wt%, cap upper surface ware are heated in heating slightly boiling 30min on low temperature electric hot plate
It is 10mL to add water management volume at any time in the process, removes, is rinsed with water surface plate and wall of cup, is cooled to room temperature, use slow filter paper
All undissolved samples are moved on filter paper, are washed to no chlorion by filtering, and precipitation is placed in 50mL porcelain together with filter paper
In crucible, heat up ashing is placed in high temperature furnace after low temperature drying, in 700 DEG C of calcination 30min, taking-up is cooled to room temperature, is transferred to
Weighing disk weigh calcination amount of substance, 0.2000g is added with high purity aluminium oxide, is placed in former crucible, weigh 6.0000g flux,
0.5g ammonium nitrate in crucible, flux by 67wt% Li2B4O7With the LiBO of 33wt%2Composition, stirs evenly, is transferred to platinum-gold
In crucible, add saturation lithium-bromide solution 0.4mL, in 650 DEG C of pre-oxidation 3min on high frequency fusion machine, 1075 DEG C melt 2min, add
Ammonium iodide 20mg shakes melting 4.5min, then adds ammonium iodide 20mg, pours into warmed-up platinum-gold after shake melting 1.5min and closes
In golden mold, poured out after being cooled to room temperature；
B. assay：It will be cooled to that room temperature, treated, and sample is placed in XRF spectrometer sample introduction exchangers measures：
Instrument and equipment：Axios sequential scan formulas wavelength dispersion X-ray fluorescence spectrometer (Dutch PANalytical companies),
The super sharp rhodium palladium X-ray tube of ceramic thin beryllium end window (75um), SuperQ4.0 quantitative analysis softwares；II type recirculated cooling waters of BLK-
System (Beijing Zhonghe Chuangye Science ＆ Technology Development Co., Ltd)；Domestic intelligent high frequency melts model machine (the more limited public affairs of woods electric appliance in Chengdu
Department)；Platinum yellow alloy crucible.
Standard series：Standard curve, barite country mark are made with national standard substance and the calibration sample manually prepared
Quasi- substance：GBW07811~GBW07817, rock national standard substance GBW07111, GBW07132, high-purity BaSO4, Yi Jiren
The calibration sample that work is prepared does standard series；
Instrument operating condition：According to the property of barium element, to the analysis condition of main preservation element and barium in barite into
Selection is gone：
Current/voltage：Barium and light element select low-voltage, high current；
Collimator：Barium and light element select thick collimator；
Optical filter：Bromine, strontium, zinc select Al optical filters, reduce scattering background, eliminate miscellaneous line interference；Barium and other elements choosing
It selects free of light filter；
Peak angle：It is scanned with barite samples prepared by fuse piece method, the peak position obtained according to scanning determines peak value
Angle；
Background dot：The background dot selection of barium, strontium, bromine, zinc, sulphur, silicon is in long wave side；Iron, titanium, calcium, potassium, aluminium background click
It selects in shortwave side；Respectively there are one background dots in the long shortwave both sides of spectral peak for magnesium, sodium；
PHD：To filter out influence of the interference spectral line to barium element, makees PHD distribution occasion inspections, determine PHD upper lower limit values；
Time of measuring：Time of measuring is determined according to the accuracy requirement of the property of element and measurement；
With Fe2O3、SiO2, CaO content and Zn the intensity of spectral line correction after, parameter of curve is obviously improved, the survey of standard substance
It is small to determine resultant error, selection participates in correction.This law measures selection without internal standard.
C. testing result：Detection is limited to 0.0087%, and measurement is limited to 0.18%.
In order to verify the methodological science and validity for measuring barium sulfate content in barite of the present invention, this method carries out
Following verification：
1, bioassay standard substance
It comments row to measure 4 times 6 barite national standard substances, the results are shown in Table 1.
The barium sulfate measured value (%) of 1 standard substance of table
2, method compares
Select the ridges Surabaja Ding Jia fluorite type barite, highly dense king's column quartz type barite, Anqiu City village Wei Lin sulfide
70, the sample of three kinds of different types of type barite, different barium sulfate contents, the rear and gravimetric method that barium sulfate is measured with this law are surveyed
Determine result to be compared.
2 this law of table and gravimetric detemination result deck watch
The result shows that：There are 69 samples to meet code requirement, only No. 212002 failed samples in 70 samples, thus
Outer inspection has been carried out to the sample, it was demonstrated that outer inspection result is consistent with this law result, and former gravimetric method result is wrong, this law result it is accurate
Degree has also obtained further confirmation.
Claims (1)
- The method that 1.X ray fluorescence glass flux sheet methods measure barium sulfate content in barite, which is characterized in that including following step Suddenly：A. sample pre-treatment：The accurate sample 0.2000g weighed in 105 DEG C of dry 2h, is placed in 50mL beakers, adds The hydrochloric acid of 10mL10wt%, the nitric acid of 4mL10wt%, cap upper surface ware are heated in heating slightly boiling 30min on low temperature electric hot plate It is 10mL to add water management volume at any time in the process, removes, is rinsed with water surface plate and wall of cup, is cooled to room temperature, use slow filter paper All undissolved samples are moved on filter paper, are washed to no chlorion by filtering, and precipitation is placed in 50mL porcelain together with filter paper In crucible, heat up ashing is placed in high temperature furnace after low temperature drying, in 700 DEG C of calcination 30min, taking-up is cooled to room temperature, is transferred to Weighing disk weigh calcination amount of substance, 0.2000g is added with high purity aluminium oxide, is placed in former crucible, weigh 6.0000g flux, 0.5g ammonium nitrate stirs evenly in crucible, is transferred in platinum-gold crucible, adds saturation lithium-bromide solution 0.4mL, in high frequency fusion machine Upper 650 DEG C of pre-oxidation 3min, 1075 DEG C of melting 2min add ammonium iodide 20mg, shake melting 4.5min, then add ammonium iodide 20mg, It pours into warmed-up platinum-gold alloy mold after shaking melting 1.5min, is poured out after being cooled to room temperature；The flux by The Li of 67wt%2B4O7With the LiBO of 33wt%2Composition；B. assay：It will be cooled to that room temperature, treated, and sample is placed in XRF spectrometer sample introduction exchangers measures：Standard series：Standard curve, barite national standard object are made with national standard substance and the calibration sample manually prepared Matter：GBW07811~GBW07817, rock national standard substance GBW07111, GBW07132, high-purity BaSO4 and manually match The calibration sample of system does standard series；Instrument operating condition：According to the property of barium element, to strontium in barite, bromine, zinc, sulphur, silicon, iron, titanium, calcium, potassium, aluminium, magnesium, The analysis condition of sodium and barium is selected：Current/voltage：Barium and magnesium, sodium, titanium, silicon, sulphur, calcium, potassium, aluminium select low-voltage, high current；Collimator：Barium and magnesium, sodium, titanium, silicon, sulphur, calcium, potassium, aluminium select thick collimator；Optical filter：Bromine, strontium, zinc select Al optical filters, reduce scattering background, eliminate miscellaneous line interference；Barium and sulphur, silicon, iron, titanium, calcium, Potassium, aluminium, magnesium, sodium selection are free of light filter；Peak angle：It is scanned with barite samples prepared by fuse piece method, the peak position obtained according to scanning determines peak angle；Background dot：The background dot selection of barium, strontium, bromine, zinc, sulphur, silicon is in long wave side；The background dot selection of iron, titanium, calcium, potassium, aluminium exists Shortwave side；Respectively there are one background dots in the long shortwave both sides of spectral peak for magnesium, sodium；PHD：To filter out influence of the interference spectral line to barium element, makees PHD distribution occasion inspections, determine PHD upper lower limit values；Time of measuring：Time of measuring is determined according to the accuracy requirement of the property of element and measurement；C. testing result：Detection is limited to 0.0087%, and measurement is limited to 0.18%.
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| CN109738246A (en) * | 2018-12-14 | 2019-05-10 | 核工业北京地质研究院 | A kind of sulfide ore high-temperature fusion method |
| CN110530852B (en) * | 2019-10-16 | 2021-03-19 | 国家地质实验测试中心 | Method for analyzing barite by mixed flux decomposition inductively coupled plasma spectrometer |
| CN113514599A (en) * | 2021-03-25 | 2021-10-19 | 长沙矿冶研究院有限责任公司 | Method for measuring content of barium sulfate in ore |
| CN113820342A (en) * | 2021-09-09 | 2021-12-21 | 台州高视通智能科技有限公司 | Trace element X-ray fluorescence measuring method and device and electronic equipment |
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