CN109406497A - The measuring method of component content in ladle refining furnace high-efficiency reducing agent - Google Patents
The measuring method of component content in ladle refining furnace high-efficiency reducing agent Download PDFInfo
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- CN109406497A CN109406497A CN201811614807.9A CN201811614807A CN109406497A CN 109406497 A CN109406497 A CN 109406497A CN 201811614807 A CN201811614807 A CN 201811614807A CN 109406497 A CN109406497 A CN 109406497A
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- titer
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Abstract
The present invention provides a kind of measuring methods of component content in ladle refining furnace high-efficiency reducing agent.Ladle refining furnace high-efficiency reducing agent includes metallic aluminium, aluminium oxide, calcium oxide, silica and magnesia, measuring method includes: that the mixture of part ladle refining furnace high-efficiency reducing agent and flux is placed in the ceramic crucible at graphite pads bottom to melt, and obtains molten liquid；Spectrum analysis is carried out to molten liquid using the emission spectrometer of inductively coupled plasma body, obtains the content of aluminium oxide, calcium oxide, silica and magnesia.This method chemical reagent easy to operate, at low cost, using is few, with high accuracy, meets the demand of fast pace production.
Description
Technical field
The present invention relates to analytical chemistry fields, contain in particular to ingredient in a kind of ladle refining furnace high-efficiency reducing agent
The measuring method of amount.
Background technique
LF high-efficiency reducing agent is fritting for one of ladle refining furnace deoxygenation of liquid steel and the important auxiliary material of desulfurization, is mainly used for
To improve the inherent quality of steel, adjustment steel slag basicity clean with sharp slag making for deoxidization desulfuration in steelmaking process, refines crystal grain, raising
The intensity and low-temperature flexibility of steel.Common LF high-efficiency reducing agent in STEELMAKING PRODUCTION is to have metallic aluminium, aluminium oxide (Al mostly2O3)、
Calcium oxide (CaO), silica (SiO2) and magnesia (MgO) the above components in certain proportion be combined with activator, fluxing agent.
In order to meet the needs of different type steel-smelting production process and evaluate the quality of LF high-efficiency reducing agent, need in reducing agent
Primary and secondary quantitative elements content is accurately measured.Both have containing metallic aluminium containing aluminium oxide in LF high-efficiency reducing agent, it is presently used
Method be all the content for measuring full aluminium, the i.e. total amount of metallic aluminium and aluminium oxide.Really play deoxidation in reducing agent is gold
Belong to aluminium, wherein metal aluminum content is according to the difference of manufacturer, and the price of metallic aluminium is ten times of aluminium oxide, therefore is passed through
The real content that detection means accurately quickly analyzes metallic aluminium in LF high-efficiency reducing agent is extremely important.Convenient and Accurate Determining is also
Effective component-metallic aluminium content in former agent not only contributes to iron and steel metallurgy enterprise and improves process for making and reduce cost,
Steel product quality is promoted, while being of great significance to the friction for avoiding trade both sides.
Currently, the analysis of the such material of LF high-efficiency reducing agent there is no national standard, machinery industry standard JB/T5204-2007
" silicon carbide deoxidier chemical analysis method " uses potassium fluosilicate titration measuring SiO2, spectrophotometry Fe2O3With P, EDTA
Titration measuring CaO and MgO, complexometric titration Al2O3.The analysis of metal aluminum content currently without the method published,
Document report both domestic and external is also in the majority with single element analysis, mostly uses gravimetric method, x ray fluorescence spectrometry, spectrophotometry greatly
Deng, the high realistic problem of generally existing detection cycle length, trivial operations, analysis cost, it is not able to satisfy quickly high-volume analysis and surveys
The requirement of examination.Also there is component content in inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis deoxidier at present
Report, but it is most of using sour molten-inductively coupled plasma atomic emission spectrometry, also have alkali fusion-electricity of use in the recent period
Feel coupled plasma optical emission spectroscopic methodology, is all to be not suitable for containing metal simple-substance class using platinum crucible and nickel crucible or iron crucible
The melting of material, therefore it is not able to satisfy the testing requirements of LF high-efficiency reducing agent content.
Find in actual operation the deoxidiers of many types through acid dissolution not fully, especially aluminium measurement result is inclined
It is low；On the other hand it since silicone content cannot be measured simultaneously using acid extracting processing sample, and needs again using silica weight
Amount method or potassium fluosilicate titration individually measure silicon.In order to improve accuracy and the detection efficiency of analyzing measurement in real work,
Realize that measurement must use alkali fusion-inductively coupled plasma emission spectrography while aluminium, silicon.And currently used alkali fusion-
Inductively coupled plasma emission spectrography cannot be melted and be contained containing such using platinum crucible and nickel crucible or iron crucible
Have the oxidation category material of metal simple-substance, not so material and metallic crucible alloying and corrode crucible.
Summary of the invention
The main purpose of the present invention is to provide a kind of measuring method of component content in ladle refining furnace high-efficiency reducing agent,
There are complicated for operation when solving to be measured component content in ladle refining furnace high-efficiency reducing agent using existing analysis method
With problem at high cost.
To achieve the goals above, according to the present invention to provide component content in a kind of ladle refining furnace high-efficiency reducing agent
Measuring method, ladle refining furnace high-efficiency reducing agent includes metallic aluminium, aluminium oxide, calcium oxide, silica and magnesia, measurement
Method includes: that the mixture of part ladle refining furnace high-efficiency reducing agent and flux is placed in the ceramic crucible at graphite pads bottom to carry out
Melting, obtains molten liquid；Spectrum analysis is carried out to molten liquid using the emission spectrometer of inductively coupled plasma body, is aoxidized
The content of aluminium, calcium oxide, silica and magnesia.
Further, flux be sodium carbonate and boric acid mixture, it is preferable that the weight ratio of sodium carbonate and boric acid be (2~
3):1。
Further, the weight ratio of part ladle refining furnace high-efficiency reducing agent and flux is 1:(20~40).
Further, melting step includes: that mixture is carried out watery fusion in the ceramic crucible at graphite pads bottom, is obtained
First molten product, wherein the temperature of watery fusion process is 700~800 DEG C, and the time is 5~10min；By the first molten product
High-temperature fusion is carried out, obtains the second molten product, the temperature of high-temperature fusion process is 900~950 DEG C, the melting time is 10~
30min；Second molten product and aqueous hydrochloric acid solution are subjected to acidleach, then in turn through filtering and filtrate constant volume process, obtained
Molten liquid；Preferably, by hydrochloric acid, 1:1 is mixed to get aqueous hydrochloric acid solution by volume with water.
Further, during acidleach, every addition 0.1000g ladle refining furnace high-efficiency reducing agent, the use of aqueous hydrochloric acid solution
Amount is 20~40mL.
Further, the step of spectrum analysis includes: the silica titer for preparing various concentration respectively, measures dioxy
The intensity of emission spectra of element silicon in SiClx titer, and using the concentration of silica titer as ordinate, analytical line intensity
Than drawing the first working curve for abscissa；The calcium oxide titer for preparing various concentration respectively, measures in calcium oxide titer
The intensity of emission spectra of calcium constituent, and using the concentration of calcium oxide titer as ordinate, analytical line intensity ratio is abscissa, is drawn
Second working curve；The aluminium element titer for preparing various concentration respectively, measures the transmitting light of aluminium element in aluminium element titer
Spectral intensity, and using the concentration of aluminium element titer as ordinate, analytical line intensity ratio is abscissa, draws third working curve；
The magnesia titer for preparing various concentration respectively, measures the intensity of emission spectra of magnesium elements in magnesia titer, and with oxygen
The concentration for changing magnesium titer is ordinate, and analytical line intensity ratio is abscissa, draws the 4th working curve；Measure aluminium in molten liquid
Element, calcium constituent, magnesium elements and element silicon emitted luminescence intensity ratio, by the first working curve, the second working curve, third work
Curve and the 4th working curve calculate the content of aluminium oxide, calcium oxide, silica and magnesia, are indicated with μ g/mL or %.
Further, before carrying out spectrometry procedure, spectrometry procedure further includes by inductively coupled plasma body
Emission spectrometer preheated, time of warm is 20~40min.
Further, in spectrometry procedure, select following analysis condition: the wavelength of element silicon analytical line is
212.412nm and 251.612nm, the wavelength of calcium constituent analytical line are 183.801nm and 315.887nm, aluminium element analytical line
Wavelength is 396.152nm, and the wavelength of magnesium elements analytical line is 383.826nm.
Further, measuring method further include: in the absence of air conditions, make ferrum sulfuricum oxydatum solutum and remaining ladle essence
Furnace high-efficiency reducing agent carries out redox reaction, obtains redox products；Phosphoric acid and two is added into redox products
Anilinesulfonic acid sodium is incorporated to the titration of potassium bichromate standard solution to terminal, records the volume of the potassium bichromate standard solution of consumption；And
According to the volume of the potassium bichromate standard solution of consumption, the content of the metallic aluminium in ladle refining furnace high-efficiency reducing agent is calculated.
Further, the temperature of redox reaction process is 80~100 DEG C, and heating time is 90~120min.
It applies the technical scheme of the present invention, in melting process, using the ceramic crucible at graphite pads bottom as melting process
Reacting environment can overcome metallic element in ladle refining furnace high-efficiency reducing agent (LF high-efficiency reducing agent) that melting occurs and corrodes earthenware
The problem of crucible, this makes it possible to using crucible melting-inductively coupled plasma emission spectrography, while measurement contains metallic aluminium
Aluminium oxide (Al in the ladle refining furnace high-efficiency reducing agent (LF high-efficiency reducing agent) of class2O3), calcium oxide (CaO), silica
(SiO2) and magnesia (MgO) content, and metallic aluminium can be measured directly using existing analysis method.This method is easy to operate,
Chemical reagent that is at low cost, using is few, with high accuracy, meets the demand of fast pace production.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, using existing analysis method to component content in ladle refining furnace high-efficiency reducing agent
There is a problem of when being measured complicated for operation and at high cost.In order to solve the above-mentioned technical problem, this application provides a kind of steel
The measuring method of component content in packet refining furnace high-efficiency reducing agent, ladle refining furnace high-efficiency reducing agent include metallic aluminium, aluminium oxide,
Calcium oxide, silica and magnesia, measuring method include: by the mixture of part ladle refining furnace high-efficiency reducing agent and flux
It is placed in the ceramic crucible at graphite pads bottom and is melted, obtain molten liquid；Using the emission spectrometer of inductively coupled plasma body
Spectrum analysis is carried out to molten liquid, obtains the content of aluminium oxide, calcium oxide, silica and magnesia.
In above-mentioned melting process, steel can be overcome as the reacting environment of melting process using the ceramic crucible at graphite pads bottom
The problem of metallic element occurs melting and corrodes crucible in packet refining furnace high-efficiency reducing agent (LF high-efficiency reducing agent), this makes it possible to
Using crucible melting-inductively coupled plasma emission spectrography, while it is efficient to measure the ladle refining furnace containing metallic aluminium class
Aluminium oxide (Al in reducing agent (LF high-efficiency reducing agent)2O3), calcium oxide (CaO), silica (SiO2) and magnesia (MgO)
Content, and metallic aluminium can be measured directly using existing analysis method.This method is easy to operate, the at low cost, chemical reagent that uses
Less, with high accuracy, meet the demand of fast pace production.
In above-mentioned melting process, flux can select type commonly used in the art.Preferably, flux is sodium carbonate and boric acid
Mixture.The molten of ladle refining furnace high-efficiency reducing agent is advantageously reduced as flux using the mixture of above two flux
Point, to be conducive to shorten the melting time.In order to further increase melting effect, it is highly preferred that the weight of sodium carbonate and boric acid
Than for (2~3): 1.
In a kind of preferred embodiment, in melting process, the weight ratio of ladle refining furnace high-efficiency reducing agent and flux is
1:(20~40).The weight ratio of ladle refining furnace high-efficiency reducing agent and flux includes but is not limited to above range, and is limited
Be conducive to further increase the melting efficiency of ladle refining furnace high-efficiency reducing agent within the above range.
In a kind of preferred embodiment, melting step includes: the mixing by ladle refining furnace high-efficiency reducing agent and flux
Object carries out watery fusion in the ceramic crucible at graphite pads bottom, obtains the first molten product, wherein the temperature of watery fusion process
It is 700~800 DEG C, the time is 5~10min；First molten product is subjected to high-temperature fusion, obtains the second molten product, high temperature
The temperature of melting process is 900~950 DEG C, and the melting time is 10~30min；Second molten product and aqueous hydrochloric acid solution are carried out
Acidleach obtains molten liquid then in turn through filtering and filtrate constant volume process.In melting process, watery fusion process is first carried out
In advantageously reduce the probability to splash in melting process, and under above-mentioned technological parameter carry out high-temperature fusion process be conducive to
It is as much as possible molten liquid by the conversion in ladle refining furnace high-efficiency reducing agent, to be conducive to improve testing result
Accuracy.Preferably, by hydrochloric acid, 1:1 is mixed to get aqueous hydrochloric acid solution by volume with water.Preferably, in order to further prevent melting
Splashing process during melting, before carrying out watery fusion process, first using filter paper by ladle refining furnace high-efficiency reducing agent with
The mixture of flux encases, and then carries out watery fusion process again.By watery fusion process above-mentioned temperature range carry out into
It while row melting process, also can gradually make filter paper that ashing volatilization occur, influence subsequent high temperature frit reaction to avoid filter paper
It carries out.
During improving acidleach, the dissolution rate of molten product, it is preferable that during acidleach, every addition 0.1000g steel
Packet refining furnace high-efficiency reducing agent, the dosage of aqueous hydrochloric acid solution are 20~40mL, preferably 30mL.
Usually need first to prepare silica titer, calcium oxide titer, aluminium element mark before carrying out above-mentioned test
Quasi- liquid and magnesia titer, above-mentioned several titers can be prepared using method commonly used in the art.
In a kind of preferred embodiment, prepare silica titer the step of include: make weight percentage >=
99.99% silica after calcination 30min~1h, is cooled to room temperature at 950~1000 DEG C；By 1.0000g silica
With the mixture (natrium carbonicum calcinatum and boric acid being mixed to get by weight for 2:1) of 3g natrium carbonicum calcinatum be placed in platinum crucible
In, (1~2) g natrium carbonicum calcinatum mixture is then covered on said mixture；Platinum lid (staying a gap) is covered by platinum crucible
Heating melting continues heating melting 3min, obtains siliceous frit to transparent in the high temperature furnace for being placed in 950 DEG C；By siliceous frit
It is transferred in the polytetrafluoroethylene beaker for fill cold water and leaches after cooling, low-temperature heat to above-mentioned siliceous frit is completely dissolved.It will
Solution moves into 1000mL volumetric flask, is diluted with water to scale, mixes, obtains silica titer, stores in polypropylene or poly-
In tetrafluoroethene bottle.1mL contains 1000.0 μ g silica in this solution.
In a kind of preferred embodiment, prepare calcium oxide titer the step of include: to make calcium carbonate at 105~110 DEG C
It dries to constant weight；1.7848g calcium carbonate is mixed in the beaker of 300mL with 20mL water, obtains mixed liquor；To above-mentioned mixed liquor
Middle addition aqueous hydrochloric acid solution (1:1 is mixed hydrochloric acid by volume with water) boils removing carbon dioxide to being completely dissolved, after cooling,
It moves into 1000mL volumetric flask, is diluted simultaneously constant volume with water, obtains the oxidation standard calcium that calcium constituent concentration is 1000.0 μ g/mL
Liquid.
In a kind of preferred embodiment, prepare aluminium element titer the step of include: l.0000g weight percentage be
At the metallic aluminium of 99.99wt%, 50mL aqueous hydrochloric acid solution (1:1 is mixed hydrochloric acid by volume with water) and 40~60 DEG C of 10mL nitric acid
After heating for dissolving, it is cooled to room temperature and moves into 1000mL volumetric flask, be diluted with water to scale, shake up, obtain aluminium element titer.
This solution 1mL aluminium element containing 1mg.The rate of dissolution that nitric acid is conducive to improve metallic aluminium is added in course of dissolution, shortens titer
The preparation time.
In a kind of preferred embodiment, the step of preparation magnesia titer includes: to weigh 0.5000g to exist in advance respectively
The magnesia (standard reagent) of 1000 DEG C of calcinations adds 10mL hydrochloric acid solution, reaction solution is moved into 1000mL in 150mL beaker
In volumetric flask, it is diluted with water to scale, mixes, obtains magnesia titer.This solution 1mL contains 500.0 μ g magnesia.
The ladle refining furnace high-efficiency reducing agent containing metallic aluminium class can be measured simultaneously using the above method, and (LF is efficiently restored
Agent) in aluminium oxide (Al2O3), calcium oxide (CaO), silica (SiO2) and magnesia (MgO) content, and this method have behaviour
Make the advantages that chemical reagent that is simple, at low cost, using is few, with high accuracy.Preferably, the step of spectrum analysis includes:
The silica titer for preparing various concentration respectively measures the intensity of emission spectra of element silicon in silica titer, and
Using the concentration of silica titer as ordinate, analytical line intensity ratio is abscissa, draws the first working curve；
The calcium oxide titer of various concentration is prepared respectively, and the emission spectrum for measuring calcium constituent in calcium oxide titer is strong
Degree, and using the concentration of calcium oxide titer as ordinate, analytical line intensity ratio is abscissa, draws the second working curve；
The aluminium element titer of various concentration is prepared respectively, and the emission spectrum for measuring aluminium element in aluminium element titer is strong
Degree, and using the concentration of aluminium element titer as ordinate, analytical line intensity ratio is abscissa, draws third working curve；
The magnesia titer of various concentration is prepared respectively, and the emission spectrum for measuring magnesium elements in magnesia titer is strong
Degree, and using the concentration of magnesia titer as ordinate, analytical line intensity ratio is abscissa, draws the 4th working curve；
The emitted luminescence intensity ratio for measuring aluminium element, calcium constituent, magnesium elements and element silicon in molten liquid, it is bent by the first work
Line, the second working curve, third working curve and the 4th working curve calculate aluminium oxide, calcium oxide, silica and oxidation
The content of magnesium is indicated with μ g/mL or %.The accuracy that spectrum test is conducive to improve testing result is carried out by the above method.
In order to further increase the accuracy of testing result, it is preferable that the related coefficient of above-mentioned working curve is greater than
0.999。
In a kind of preferred embodiment, before carrying out spectrometry procedure, spectrometry procedure further includes by inductance
The emission spectrometer of coupled plasma is preheated, and the time of warm is 20~40min.Carrying out spectrum analysis test
Before, first the emission spectrometer of inductively coupled plasma body is preheated, instrument can be made to reach preferably working condition, from
And be conducive to improve the accuracy of testing result.
The selection of element wavelength to be measured mainly considers the factors such as its sensitivity and background interference.From instrument analytical line database
In transfer the higher spectral line of analytical line medium sensitivity, with standard solution simulation test liquid, successively in central wavelength environs
It is scanned, low with background, signal-to-noise ratio is high, high sensitivity, each element spectrogram is that principle selection is each there is no overlap of spectral lines interference
The analysis of line wavelength of element to be measured.Preferably, in spectrometry procedure, following analysis condition: the wave of element silicon analytical line is selected
A length of 212.412nm and 251.612nm, the wavelength of calcium constituent analytical line are 183.801nm and 315.887nm, aluminium element analysis
The wavelength of line is 396.152nm, and the wavelength of magnesium elements analytical line is 383.826nm.
The content of metallic aluminium can be detected using oxidimetry in ladle refining furnace high-efficiency reducing agent.One
In kind preferred embodiment, said determination method further include: in the absence of air conditions, make ferrum sulfuricum oxydatum solutum and remaining steel
Packet refining furnace high-efficiency reducing agent carries out redox reaction, obtains redox products；Phosphoric acid is added into redox products
And diphenylamine sulfonic acid sodium salt, it is incorporated to the titration of potassium bichromate standard solution to terminal, records the body of the potassium bichromate standard solution of consumption
Product；And the volume of the potassium bichromate standard solution according to consumption, calculate containing for the metallic aluminium in ladle refining furnace high-efficiency reducing agent
Amount.
In a kind of preferred embodiment, the temperature of redox reaction process is 80~100 DEG C, heating time is 90~
120min.The temperature of redox reaction process and heating time include but is not limited to above range, and are limited to above-mentioned
Be conducive to further increase aluminium element in ladle refining furnace high-efficiency reducing agent in range and be converted into aluminum ions conversion ratio, to have
Conducive to the accuracy further increased to the testing result of metallic aluminium.
Embodiment 1
1, the preparation of titer.
(1) silica standard solution
Weighing 1.0000g silica, (mass fraction is greater than 99.9%, in advance after 1000 DEG C of calcination 1h, is placed in drying
In device, it is cooled to room temperature), it is placed in the platinum crucible added with 3g natrium carbonicum calcinatum, stirs evenly, it is anhydrous to cover (1-2) g again above
Sodium carbonate first heats platinum crucible at low temperature, then is placed at 950 DEG C of high temperature heating melting to transparent, continues heating melting
3min takes out, cooling.It moves into the polytetrafluoroethylene beaker for filling cold water and leaches, low-temperature heat to frit is completely dissolved.It takes out
Crucible is carefully cleaned, is cooled to room temperature, and solution is moved into 1000mL volumetric flask, scale is diluted with water to, and is mixed, is stored in poly-
In propylene or polytetrafluoroethylene (PTFE) bottle.This solution 1mL contains 1000.0 μ g silica.
(2) calcium oxide standard liquid
1.7848g is weighed in advance in the 105-110 DEG C of dry calcium carbonate to constant weight in 300mL beaker, 20mL water is added,
Aqueous hydrochloric acid solution (volume ratio of hydrochloric acid and water is 1:1) is slowly added into being completely dissolved, removing carbon dioxide is boiled, removes cold
But, it moves into 1000mL volumetric flask, is diluted with water to scale, shakes up.This solution 1mL contains 1000.0 μ g calcium oxide.
(3) aluminium element standard solution
Fine aluminium (99.99) is weighed l.0000g in beaker, adding aqueous hydrochloric acid solution, (volume ratio of hydrochloric acid and water is 1:1) 50m
L is cooled to room temperature and moves into 1 liter of volumetric flask, be diluted with water to scale, shake up after nitric acid 10mL low-temperature heat dissolution.This solution
1mL aluminium containing 1mg.
(4) magnesia standard liquid
The magnesia (standard reagent) of the 0.5000g calcination at 1000 DEG C in advance is weighed in 150mL beaker, adds 10mL salt
Acid solution moves into 1000mL volumetric flask, is diluted with water to scale, mixes.This solution 1mL contains 500.0 μ g magnesia.
2, instrument analysis detection
Ladle refining furnace high-efficiency reducing agent is detected using the emission spectrometer of inductively coupled plasma body, can be made
Measurement type, analytical line are shown in Table 1 with single-channel scanning type or simultaneously.
Table 1
Curve negotiating calculates related coefficient to examine.Related coefficient should be greater than 0.999.
Specific test method is as follows:
(1) melting of sample: weighing 0.1000g ladle refining furnace high-efficiency reducing agent, is placed in and is placed with 3g mixed flux (carbonic acid
The mixture of sodium and boric acid, weight ratio 2:1) it is converted on half quantitative filter paper of triangle and mixes, glomeration is packed tightly, is put into pre-
First in the rebasing 50mL porcelain crucible of graphite powder, 8min is melted at 750 DEG C, then melt 20min at 900 DEG C, it is cooling, use tweezer
Frit taking-up is swept net graphite powder by son；Above-mentioned frit is put into fill 30mL aqueous hydrochloric acid solution (volume of hydrochloric acid and water be 1:
1) in, and 15min is heated at 50 DEG C, filtered, constant volume obtains sample solution in 250mL volumetric flask.
(2) foundation of standard curve:
5.00,10.00,20.00,25.00,50.00mL aluminium element standard solution are pipetted respectively；
5.00,10.00,20.00,25.00,40.00mL calcium oxide standard liquid；
1.00,2.00,4.00,5.00,10.00mL silica standard solution；
1.00,2.00,5.00,10.00,20.00mL magnesia standard liquid；
Five kinds of hybrid standard liquids are prepared respectively from low to high by constituent content, are successively added in above-mentioned five kinds of mixed standard solutions
Enter 20mL aqueous hydrochloric acid solution (volume of hydrochloric acid and water is 1:1), and be diluted to scale (250ml volumetric flask) with water, is mixed.
If the first hybrid standard liquid is 5.00mL aluminium element standard solution, 5.00mL calcium oxide standard liquid, 1.00mL bis-
The aqueous hydrochloric acid solution of silica standard solution and 1.00mL magnesia standard liquid and 20mL (volume of hydrochloric acid and water is 1:1)
After mixing, 250mL is settled to water.
Start inductive coupling plasma emission spectrograph, and preheat 30min, illustrates to carry out instrument optimization by instrument.
Prepare for measuring analytical line and interior target emitted luminescence intensity than, the software of average value and relative standard deviation.
Measure the intensity of emission spectra of aluminium, calcium, magnesium and silicon in above-mentioned five kinds of hybrid standard liquids from low to high by constituent content
Than using the concentration of aluminium element, calcium oxide, magnesia and silica as ordinate, analytical line intensity ratio is abscissa, draws work
Make curve.
(3) measurement of sample solution
According in this method measurement oxide relevant criterion sample GBW01703, YSBC18709-05, GBW03102a
Al2O3、CaO、MgO、SiO2As a result it see the table below.By table as it can be seen that its measured value and asserting value coincide preferably, relative error is 0.40
Between~4.50%.Test result such as table 2.
Table 2
As can be seen from Table 2 using method provided by the present application standard sample is measured when, measurement result it is opposite
Error is smaller.
Ladle refining furnace high-efficiency reducing agent sample is configured to solution, and measures the hair of aluminium in sample solution, calcium, magnesium and silicon
Light strength ratio is penetrated, aluminium oxide (Al is calculated by working curve2O3), calcium oxide (CaO), silica (SiO2) and magnesia
(MgO) concentration, is indicated with %.Guarantee that the related coefficient of working curve should be greater than 0.999.Test result shows ladle refining furnace
Aluminium oxide (Al in high-efficiency reducing agent sample2O3), calcium oxide (CaO), silica (SiO2) and magnesia (MgO) concentration according to
It is secondary are as follows: 33.83wt%, 20.23.wt%, 2.42wt% and 4.53wt%.
(4) in ladle refining furnace high-efficiency reducing agent the content of metallic aluminium measurement.
0.1000gLF high-efficiency reducing agent is weighed, is placed in the dry triangular flask of 300ml.50ml ferrum sulfuricum oxydatum solutum is added
(200g/L) is placed in 90~120min of slightly boiled heating on electrothermal furnace and (is guaranteed in sample with the bottleneck beyond the Great Wall of the rubber stopper with conduit
Metallic aluminium all dissolves).It removes, clogs bottleneck with rubber stopper at once, flowing water is cooled to room temperature.10ml is added to above-mentioned triangular flask
5 drops diphenylamine sulfonic acid sodium solution (0.5%) are added dropwise in phosphoric acid, and being titrated to purple with potassium bichromate standard solution (0.1M) is terminal.
Write down the potassium bichromate volume v of consumption.
4 parallel titration processes are carried out, while the weight percent for measuring metallic aluminium in ladle refining furnace high-efficiency reducing agent contains
Amount is followed successively by 16.19wt%, 16.25wt%, 16.05wt%, 16.30wt%, and calculating average value is 16.20%.
Embodiment 2
With the difference of embodiment 1 are as follows: the weight ratio of test sample GBW01703, sodium carbonate and boric acid is 1:1.
Test result shows aluminium oxide (Al in above-mentioned test sample2O3), the concentration of calcium oxide (CaO) and magnesia (MgO)
It is followed successively by 11.98wt%, 39.86wt%, 6.85wt%.Thus compared to embodiment 1, the error of test result in the embodiment
Larger, accuracy is lower.
Embodiment 3
With the difference of embodiment 1 are as follows: test sample GBW01703, part ladle refining furnace high-efficiency reducing agent and flux
Weight ratio is 1:50.
Test result shows aluminium oxide (Al in GBW017032O3), the concentration of calcium oxide (CaO) and magnesia (MgO) successively
For 11.75wt%, 39.68wt%, 6.81wt%.Thus compared to embodiment 1, in the embodiment error of test result compared with
Greatly, accuracy is lower.
Embodiment 4
With the difference of embodiment 1 are as follows: test sample GBW01703, in melting process, the temperature of watery fusion process is
650 DEG C, time 15min；The temperature of high-temperature fusion process is 1000 DEG C, melting time 10min.
Test result shows aluminium oxide (Al in GBW017032O3), the concentration of calcium oxide (CaO) and magnesia (MgO) successively
For 12.10wt%, 40.42wt%, 7.01wt%.Thus compared to embodiment 1, in the embodiment error of test result compared with
Greatly, accuracy is lower.
Embodiment 5
With the difference of embodiment 1 are as follows: the weight ratio of test sample YSBC18709-05, sodium carbonate and boric acid is 1:1.
Test result shows silica (SiO in YSBC18709-052) concentration be followed successively by 4.89wt%.Thus compare
The error of test result is larger in embodiment 1, the embodiment, and accuracy is lower.
Embodiment 6
With the difference of embodiment 1 are as follows: test sample YSBC18709-05, part ladle refining furnace high-efficiency reducing agent and molten
The weight ratio of agent is 1:50.
Test result shows silica (SiO in YSBC18709-052) concentration be 4.78wt%.Thus compared to reality
Example 1 is applied, the error of test result is larger in the embodiment, and accuracy is lower.
Embodiment 7
With the difference of embodiment 1 are as follows: test sample YSBC18709-05, in melting process, the temperature of watery fusion process
Degree is 650 DEG C, time 15min；The temperature of high-temperature fusion process is 1000 DEG C, melting time 10min.
Test result shows silica (SiO in YSBC18709-052) concentration be 4.88wt%.Thus compared to reality
Example 1 is applied, the error of test result is larger in the embodiment, and accuracy is lower.
Comparative example 1
Test sample is GBW01703, according to machinery industry standard JB/T5204-2007 " silicon carbide deoxidier chemical analysis
Method " use complexometric titration Al2O3, EDTA titration measuring CaO and MgO concentration be followed successively by 12.45wt%,
50.45wt% and 7.31wt%.
Test sample is YSBC18709-05, according to machinery industry standard JB/T5204-2007 " silicon carbide deoxidier chemistry
Analysis method " EDTA titration measuring silica (SiO2) concentration be 5.15wt%.
Thus compared to embodiment 1, the error of test result is larger in the comparative example, and accuracy is lower.
By comparing it is found that reacting environment in melting process, using the ceramic crucible at graphite pads bottom as melting process
It can overcome the problems, such as that metallic element occurs melting and corrodes crucible in ladle refining furnace high-efficiency reducing agent (LF high-efficiency reducing agent),
This makes it possible to using crucible melting-inductively coupled plasma emission spectrography, while measuring the ladle containing metallic aluminium class
Aluminium oxide (Al in refining furnace high-efficiency reducing agent (LF high-efficiency reducing agent)2O3), calcium oxide (CaO), silica (SiO2) and oxidation
The content of magnesium (MgO), and metallic aluminium can be measured directly using existing analysis method.This method is easy to operate, it is at low cost, use
Chemical reagent is few, with high accuracy, meets the demand of fast pace production.Be conducive to improve using method provided by the present application
The accuracy of testing result.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. the measuring method of component content in a kind of ladle refining furnace high-efficiency reducing agent, which is characterized in that the ladle refining furnace
High-efficiency reducing agent includes metallic aluminium, aluminium oxide, calcium oxide, silica and magnesia, and the measuring method includes:
The mixture of the part ladle refining furnace high-efficiency reducing agent and flux is placed in the ceramic crucible at graphite pads bottom and is carried out
Melting, obtains molten liquid；
Using inductively coupled plasma body emission spectrometer to the molten liquid carry out spectrum analysis, obtain the aluminium oxide,
The content of the calcium oxide, the silica and the magnesia.
2. measuring method according to claim 1, which is characterized in that the flux is the mixture of sodium carbonate and boric acid,
Preferably, the weight ratio of the sodium carbonate and the boric acid is (2~3): 1.
3. measuring method according to claim 1 or 2, which is characterized in that the part ladle refining furnace high-efficiency reducing agent
Weight ratio with the flux is 1:(20~40).
4. measuring method according to claim 1, which is characterized in that the melting step includes:
The mixture is subjected to watery fusion in the ceramic crucible at the graphite pads bottom, obtains the first molten product, wherein
The temperature of the watery fusion process is 700~800 DEG C, and the time is 5~10min；
First molten product is subjected to high-temperature fusion, obtains the second molten product, the temperature of the high-temperature fusion process is
900~950 DEG C, the melting time is 10~30min；
Second molten product and aqueous hydrochloric acid solution are subjected to acidleach, then in turn through filtering and filtrate constant volume process, obtained
To the molten liquid；
Preferably, by hydrochloric acid, 1:1 is mixed to get the aqueous hydrochloric acid solution by volume with water.
5. measuring method according to claim 4, which is characterized in that during the acidleach, described in every addition 0.1000g
Ladle refining furnace high-efficiency reducing agent, the dosage of the aqueous hydrochloric acid solution are 20~40mL.
6. measuring method according to any one of claim 1 to 5, which is characterized in that the step of spectrum analysis wraps
It includes:
The silica titer for preparing various concentration respectively, measures the emission spectrum of element silicon in the silica titer
Intensity, and using the concentration of the silica titer as ordinate, analytical line intensity ratio is abscissa, and it is bent to draw the first work
Line；
The calcium oxide titer of various concentration is prepared respectively, and the emission spectrum for measuring calcium constituent in the calcium oxide titer is strong
Degree, and using the concentration of the calcium oxide titer as ordinate, analytical line intensity ratio is abscissa, draws the second working curve；
The aluminium element titer of various concentration is prepared respectively, and the emission spectrum for measuring aluminium element in the aluminium element titer is strong
Degree, and using the concentration of the aluminium element titer as ordinate, analytical line intensity ratio is abscissa, draws third working curve；
The magnesia titer of various concentration is prepared respectively, and the emission spectrum for measuring magnesium elements in the magnesia titer is strong
Degree, and using the concentration of the magnesia titer as ordinate, analytical line intensity ratio is abscissa, draws the 4th working curve；
The emitted luminescence intensity ratio for measuring aluminium element in the molten liquid, calcium constituent, magnesium elements and element silicon, is worked by described first
Curve, second working curve, the third working curve and the 4th working curve calculate the aluminium oxide, described
The content of calcium oxide, the silica and the magnesia is indicated with μ g/mL or %.
7. measuring method according to claim 1, which is characterized in that described before carrying out the spectrometry procedure
Spectrometry procedure further includes preheating the emission spectrometer of the inductively coupled plasma body, the warm when
Between be 20~40min.
8. measuring method according to claim 7, which is characterized in that in the spectrometry procedure, select following analysis
Condition: the wavelength of element silicon analytical line is 212.412nm and 251.612nm, the wavelength of calcium constituent analytical line be 183.801nm and
315.887nm, the wavelength of aluminium element analytical line are 396.152nm, and the wavelength of magnesium elements analytical line is 383.826nm.
9. measuring method according to claim 1, which is characterized in that the measuring method further include:
In the absence of air conditions, ferrum sulfuricum oxydatum solutum and the remaining ladle refining furnace high-efficiency reducing agent is made aoxidize also
Original reaction, obtains redox products；
Phosphoric acid and diphenylamine sulfonic acid sodium salt are added into the redox products, is incorporated to potassium bichromate standard solution and is titrated to end
Point records the volume of the potassium bichromate standard solution of consumption；And
According to the volume of the potassium bichromate standard solution of consumption, the metal in the ladle refining furnace high-efficiency reducing agent is calculated
The content of aluminium.
10. measuring method according to claim 9, which is characterized in that the temperature of the redox reaction process is 80
~100 DEG C, heating time is 90~120min.
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