CN106970100A - The method that the analysis of applied energy dispersive x-ray fluorescence determines calcium content in limestone deposit - Google Patents
The method that the analysis of applied energy dispersive x-ray fluorescence determines calcium content in limestone deposit Download PDFInfo
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- CN106970100A CN106970100A CN201710216433.4A CN201710216433A CN106970100A CN 106970100 A CN106970100 A CN 106970100A CN 201710216433 A CN201710216433 A CN 201710216433A CN 106970100 A CN106970100 A CN 106970100A
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Abstract
The invention discloses the method that a kind of analysis of applied energy dispersive x-ray fluorescence determines calcium content in limestone deposit, belong to technical field of analysis and detection, mainly solve prior art the problem of low calcium constituent launching efficiency, result low precision, not high sensitivity and low efficiency is directly detected.Limestone deposit sample is pre-processed first for this method and standard sample, the preparation of testing sample, the silver element in sample is measured with energy-dispersion X-ray fluorescence spectrometer, the characteristic peak area of silver element is detected, calibration curve is substituted into, obtains the percentage composition of silver element in sample.Further according to the stoichiometric relation of silver and calcium in sample, the content for obtaining calcium constituent in limestone deposit is calculated.The present invention realizes the measurement to calcium content in limestone deposit by indirect measuring method, with accurate, convenient, economic, easy-operating feature.
Description
Technical field
The present invention relates to technical field of analysis and detection, especially a kind of applied energy dispersive x-ray fluorescence analysis determines stone
The method of calcium content in limestone ore deposit.
Background technology
At present, the method detected for light element content in material mainly has chemical analysis and instrumental method two big
Class.Chemical analysis for different element and sample type can be divided into Ignition Lamp Method, tube oven method, gravimetric method, neutralization titration,
The specific measuring method such as colorimetric method and volumetric method.Relatively accurately light element can be carried out using common chemical method merely
Quantitative analysis, but complex steps, take longer, and need operating personnel to have compared with the chemical knowledge of horn of plenty and higher
Experiment attainment, therefore instrument analytical method increasingly favored by analyst.At present, instrument research method includes transmitting light
Spectrometry, atomic absorption spectroscopy, x-ray fluorescence analysis and plasma emlssion spectrometry etc..Wherein energy dispersion X-ray is glimmering
Light analysis (EDXRF) is the excitation apparatus by the use of X-ray tube as simple spectral line, and transmitting initial X-ray is irradiated on sample, made
Object element in sample is excited, and produces XRF and is received by a detector, obtains the energy value of object element, and with mark
The calibration curve of quasi- sample making is contrasted, and calculates the content of object element in sample, completes the quantitative analysis of element.
EDXRF methods have the advantages that analyze speed is fast, multiple element is while analyze, sample preparation requirement is low, precision is high so that this method and its
His analysis method is compared more advantageous.But the fluorescent yield, launching efficiency due to light element are relatively low, and direct Effect on Detecting is simultaneously
It is undesirable.
The content of the invention
Deficiency in terms of light element measurement is analyzed based on energy-dispersive X-ray fluorescence (EDXRF), for energy-dispersive X-ray fluorescence (EDXRF)
The problem of spectroscopic methodology detection calcium constituent sensitivity is low, the present invention provides a kind of reasonable and effective energy-dispersive X-ray fluorescence (EDXRF) point
Measuring method of the analysis applied to calcium content.
To achieve the above object, calcium in limestone deposit is determined present invention employs the analysis of applied energy dispersive x-ray fluorescence
The method of content, realizes the quantitative analysis to calcium constituent in limestone deposit using EDXRF methods.
Step one, standard sample is prepared：
a：Watery hydrochloric acid is added dropwise into limestone deposit powder first, makes the soluble substance in limestone deposit powder with the shape of ion
Formula exists in solution, as the PH=1-2 of solution, and the soluble substance in mixed solution is all dissolved in watery hydrochloric acid, and with acidity
Insoluble matter is separated；
b：Then proceed to that sodium hydroxide solution is added dropwise into solution, according to solubility product constant, control pH value, make iron in solution
Ion, aluminium ion and magnesium ion and hydroxyl react to form precipitation, and calcium stays the impurity for reacting generation in the solution in the form of an ion
Precipitation, is made up of remaining material in limestone deposit in addition to calcium constituent；
Then mixed solution is stood, filtered, dried；
Step 2, prepares testing sample：
For ensure standard sample it is similar to testing sample physicochemical properties, therefore prepare testing sample include step a, b,
C, wherein step c stand, filtered, drying preceding progress in stepb；
c：Appropriate AgNO is added dropwise into solution3Solution, reaction produces silver nitride precipitation, until precipitation is complete, in beaker
Contamination precipitation coexisted with silver nitride precipitation, wherein, AgCl quality is by NaCl and CaCl2Together decide on；It will finally mix molten
Liquid stands, filtered, drying；
Step 3, the sediment in standard sample and AgCl powder are mixed in the different ratios into graded of silver content
Close, canonical measure sample is made using powder pressing method, with energy-dispersive X-ray fluorescence (EDXRF) analysis-e/or determining canonical measure sample,
Each characteristic peak net area for making silver element in canonical measure sample is measured, using the percentage composition of silver element as abscissa, with silver
The characteristic peak net area of element is that ordinate draws calibration curve；
Step 4, it is same that the silver element in testing sample is measured with energy-dispersive X-ray fluorescence (EDXRF) analyzer, detect and treat
The characteristic peak net area of silver element in test sample product, substitutes into calibration curve, tries to achieve the percentage composition of silver element in testing sample, then root
According to silver in sample and the chemical reaction and quantitative relation of calcium, the percentage composition for obtaining limestone deposit calcium in sample element is calculated.
Enter an optimization：Composition in limestone deposit powder is CaCO3、CaO、Fe2O3、Al2O3, MgO, in step a plus
Entering the reaction equation after hydrochloric acid is：
CaCO3+2H++2Cl-=Ca2++2Cl-+H2O+CO2↑
CaO+2H++2Cl-=Ca2++2Cl-+H2O
Fe2O3+6H++6Cl-=2Fe3++6Cl-+3H2O
Al2O3+6H++6Cl-=2Al3++6Cl-+3H2O
MgO+2H++2Cl-=Mg2++2Cl-+H2O
The reaction equation after addition sodium hydroxide solution is in stepb：
Fe3++3Na++3OH-=Fe (OH)3↓+3Na+
Al3++3Na++3OH-=Al (OH)3↓+3Na+
Mg2++2Na++2OH-=Mg (OH)2↓+2Na+
AgNO is added in step c3Solution, reaction produces silver nitride precipitation, and reaction equation is：
NaCl+AgNO3=AgCl ↓+NaNO3
CaCl2+2AgNO3=Ca (NO3)2+2AgCl↓
Further optimization：In filtering, filtered with fine and close ashless quantitative filter paper with suction funnel；During drying, use
Oven drying, temperature control is precipitated at 90 DEG C after continuing 1 hour.
Beneficial effects of the present invention and feature：It can not will directly and accurately use energy-dispersive X-ray fluorescence (EDXRF) analysis measurement
In limestone deposit calcium constituent be converted into can silver element measured directly, further according to chemical equation and quantitative relation, indirectly meter
Calcium element content is calculated, measurement of the applied energy dispersive x-ray fluorescence analytic approach to calcium content in limestone deposit is realized.
Measuring speed of the invention for calcium content is fast, simple operation, with Wavelength Dispersive X-Ray Fluorescence Analysis method
(WDXRF) measurement is cost-effective compared to more economical and practical, while overcoming traditional chemical routes, time-consuming, cumbersome etc.
Drawback.The quantitative analysis to calcium constituent in limestone deposit using energy-dispersive X-ray fluorescence (EDXRF) analyzer can be effectively realized.
Brief description of the drawings
Fig. 1 is the pretreatment process figure for preparing standard sample.
Fig. 2 is the pretreatment process figure for preparing testing sample.
Fig. 3 is energy-dispersive X-ray fluorescence (EDXRF) analytic approach measured value and WDXRF results contrasts.
Embodiment
The present invention is described below with reference to Figure of description.
Limestone deposit sample is pre-processed, testing sample is prepared as shown in Figure 2：
The main component of limestone deposit is CaCO3、CaO、Fe2O3、Al2O3、MgO；
a：Appropriate watery hydrochloric acid is added dropwise into limestone deposit powder first, soluble substance is present in solution in the form of ion
In, when solution is in acid (PH=1-2), the soluble substance in solution mixed liquor is all dissolved in watery hydrochloric acid, and insoluble with acidity
Thing is separated, reaction equation：
CaCO3+2H++2Cl-=Ca2++2Cl-+H2O+CO2↑
CaO+2H++2Cl-=Ca2++2Cl-+H2O
Fe2O3+6H++6Cl-=2Fe3++6Cl-+3H2O
Al2O3+6H++6Cl-=2Al3++6Cl-+3H2O
MgO+2H++2Cl-=Mg2++2Cl-+H2O
b：Then proceed to that sodium hydroxide solution is added dropwise into solution, it is molten when pH value is between 8-10 according to solubility product constant
Iron ion, aluminium ion and magnesium ion and hydroxyl are reacted to form precipitation in liquid, and calcium is stayed in the solution in the form of an ion.Reaction generation
Sediment be remaining material in limestone deposit in addition to calcium constituent, this partly precipitated is called contamination precipitation.Its reaction equation master
Have：
Fe3++3Na++3OH-=Fe (OH)3↓+3Na+
Al3++3Na++3OH-=Al (OH)3↓+3Na+
Mg2++2Na++2OH-=Mg (OH)2↓+2Na+
c：Appropriate AgNO is added dropwise into solution3Solution, generates silver nitride precipitation, until precipitation is complete.Now in beaker
Contamination precipitation coexisted with silver nitride precipitation.From reaction equation, NaCl and CaCl2Together decide on AgCl quality.
NaCl+AgNO3=AgCl ↓+NaNO3
CaCl2+2AgNO3=Ca (NO3)2+2AgCl↓
Mixed liquor is stood, makes silver nitride precipitation sedimentation complete.Carried out with fine and close ashless quantitative filter paper with suction funnel
Filtering, then precipitated with oven drying (temperature control is at 90 DEG C or so) after 1 hour, with electronic balance weighing per group precipitation
Gross mass, then weigh a portion wait press sheet compression.
As shown in Figure 2：For the uniformity of the physical aspect and chemical composition of standard sample and testing sample, therefore in system
During standby standard sample, a~b steps of the manufacturing process of standard sample are identical with the pre-treatment step of limestone deposit sample, in c steps
In be added without silver nitrate solution, directly filtered.Now chlorion is filtered to remove completely, is wrapped in the sediment after filtering
Acid insoluble matter and the hydroxide precipitation of limy rock ore deposit.This contamination precipitation is necessarily terraced by silver content with chlorination silver powder
The ratio of degree change is mixed into many parts, and the quality for making every part of sample is 0.5g.Powder pressing method makes print.
Several pieces limestone deposit sample is equally taken, carrying out sample according to said sample processing method determines pre-treatment.Work as sample
Product add watery hydrochloric acid, soluble substance is existed in solution in the form of ion, are separated with acid not tolerant.In addition, in lime
The b steps of rock salt sample pretreatment, add sodium hydroxide solution, and adjust pH value, eliminate and are present in iron in mixture solution
Ion, aluminium ion and magnesium ion.Silver nitrate solution is added dropwise in c steps chlorion is precipitated into silver chlorate completely.Through filtering,
After drying.Weigh the sample obtained after processing, quality m successively with electronic balanceiRepresent.For convenience of measurement, Cong Zhongxuan
Appropriate quality is taken, test sample is made with powder pressing method, waits dispersive x-ray fluorescence analyzer to be measured.
In order to verify the accuracy of this method, sample making is measured for many parts using this method, and by measurement result
Average, then contrasted with WDXRF methods, comparing result is as shown in Figure 3.From figure 3, it can be seen that this method is to limestone
The measurement result of calcium content and WDXRF methods are basically identical in ore deposit, it was demonstrated that this method can be to reliably applied to calcium in limestone deposit
The measurement of content.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
Conventional method can in other embodiments be realized in the case where not departing from the marrow or scope of invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, but to accord with method disclosed herein and features of novelty is consistent
Most wide scope.
Claims (3)
1. the method that the analysis of applied energy dispersive x-ray fluorescence determines calcium content in limestone deposit, it is characterised in that：Including following
Step；
Step one, standard sample is prepared：
a：Watery hydrochloric acid is added dropwise into limestone deposit powder first, the soluble substance in limestone deposit powder is deposited in the form of ion
It is in solution, as the PH=1-2 of solution, the soluble substance in mixed solution is all dissolved in watery hydrochloric acid, and insoluble with acidity
Thing is separated；
b：Then proceed to that sodium hydroxide solution is added dropwise into solution, according to solubility product constant, control pH value, make in solution iron from
Son, aluminium ion and magnesium ion and hydroxyl are reacted to form precipitation, and calcium is stayed in the solution in the form of an ion, and the impurity of reaction generation sinks
Form sediment, it is made up of remaining material in limestone deposit in addition to calcium constituent；
Then mixed solution is stood, filtered, dried；
Step 2, prepares testing sample：
Preparing testing sample includes step a, b, c, and wherein step c stands, filtered, drying preceding progress in stepb；
c：Appropriate AgNO is added dropwise into solution3Solution, reaction produces silver nitride precipitation, until precipitation is complete, the impurity in beaker
Precipitation coexists with silver nitride precipitation, wherein, AgCl quality is by NaCl and CaCl2Together decide on；Finally mixed solution is stood,
Filtering, drying；
Step 3, the sediment in standard sample and AgCl powder are mixed in the different ratios into graded of silver content,
Canonical measure sample is made using powder pressing method, with energy-dispersive X-ray fluorescence (EDXRF) analysis-e/or determining canonical measure sample, measured
Each characteristic peak net area for making silver element in canonical measure sample, using the percentage composition of silver element as abscissa, with silver element
Characteristic peak net area for ordinate draw calibration curve；
Step 4, it is same that the silver element in testing sample is measured with energy-dispersive X-ray fluorescence (EDXRF) analyzer, detect and treat test sample
The characteristic peak net area of silver element in product, substitutes into calibration curve, the percentage composition of silver element in testing sample is tried to achieve, further according to sample
The chemical reaction and quantitative relation of silver and calcium, calculate the percentage composition for obtaining limestone deposit calcium in sample element in product.
2. the method that applied energy dispersive x-ray fluorescence analysis as claimed in claim 1 determines calcium content in limestone deposit, its
It is characterised by：Composition in limestone deposit powder is CaCO3、CaO、Fe2O3、Al2O3, MgO, in step a add hydrochloric acid after
Reaction equation is：
CaCO3+2H++2Cl-=Ca2++2Cl-+H2O+CO2↑
CaO+2H++2Cl-=Ca2++2Cl-+H2O
Fe2O3+6H++6Cl-=2Fe3++6Cl-+3H2O
Al2O3+6H++6Cl-=2Al3++6Cl-+3H2O
MgO+2H++2Cl-=Mg2++2Cl-+H2O
The reaction equation after addition sodium hydroxide solution is in stepb：
Fe3++3Na++3OH-=Fe (OH)3↓+3Na+
Al3++3Na++3OH-=Al (OH)3↓+3Na+
Mg2++2Na++2OH-=Mg (OH)2↓+2Na+
AgNO is added in step c3Solution, reaction produces silver nitride precipitation, and reaction equation is：
NaCl+AgNO3=AgCl ↓+NaNO3
CaCl2+2AgNO3=Ca (NO3)2+2AgCl↓。
3. the method that applied energy dispersive x-ray fluorescence analysis as claimed in claim 1 determines calcium content in limestone deposit, its
It is characterised by：In filtering, filtered with fine and close ashless quantitative filter paper with suction funnel；During drying, with oven drying, temperature
Degree control is precipitated at 90 DEG C after continuing 1 hour.
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| CN108226204A (en) * | 2018-01-19 | 2018-06-29 | 沈阳师范大学 | The method that the analysis of applied energy dispersive x-ray fluorescence measures chlorinity in complex fertilizer |
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