CN103018230A - Method for synchronously measuring various elements in metallurgical sundries - Google Patents
Method for synchronously measuring various elements in metallurgical sundries Download PDFInfo
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Abstract
The invention belongs to the technical field of test of metallurgical materials, and particularly relates to a method for synchronously measuring various elements in the metallurgical sundries. The method for synchronously measuring various elements in the metallurgical sundries comprises the following steps: (1) processing a sample; (2) drawing a working curve; and (3) measuring the test sample. According to the method for synchronously measuring various elements in the metallurgical sundries, the proper sample processing method is selected, the substrates are flexibly matched, and the parameters of instruments are reasonably optimized, so that the accuracy in measurement of the various elements in the metallurgical sundries under different species and wide scope can be ensured.
Description
Technical field
The invention belongs to the technical field of metallurgical material test, determination method when being specifically related in the assorted material of a kind of metallurgy multiple element.
Background technology
Alkaline metal mainly contains potassium and sodium, and blast furnace itself has certain alkaline discharging capacity, and alkaline metal is little on the blast furnace impact in range of control.But it is too many to enter stove iron ore alkali metal content, surpasses the blast furnace alkaline discharging capacity, will form the alkaline metal enrichment, very easily causes softening temperature to reduce, and moves on the cohesive zone, is unfavorable for developing indirect reduction, causes coke ratio to raise.Pelletizing contains alkaline metal and can cause the pelletizing abnormal expansion to cause serious efflorescence, worsens permeability of stock column, and alkaline metal STRENGTH ON COKE performance is destroyed also very serious.In addition, blast furnace middle and upper part alkali metal compound is attached on the furnace wall, impels that furnace wall knot is thick, dross and destroy bricking.Lead in the iron ore almost all is reduced in blast furnace, because plumbous density is large, therefore be sunken under the ladle heel layer, destructible furnace bottom brickwork joint might cause burn-through of furnace hearth.Zinc is easy to gasification, and zinc fume easily enters brickwork joint, expands after being oxidized into ZnO, destroys the upper shaft firebrick lining.Copper in the iron ore and this reduction of arsyl enter the pig iron, affect iron quality.In order to grasp the working of a furnace in the smelting process and the consumption of product quality and crude fuel, the detection data of the harmful elements such as the alkaline metal in the iron ore, lead, zinc, arsenic, copper are particularly important.
Owing to being subjected to the restriction of resources supplIes, the raw materials used middle harmful element K of iron and steel enterprise, Na, Pb, Zn, As, Cu are higher, after these harmful elements enter stove, destroy on the one hand the metallurgical performance of raw material, and formation circulation in stove, affect the optimization of the stable and index of road conditions, on the other hand furnace lining and cooling infrastructure are caused erosion, shorten the life of the blast furnace.Accurately and timely the content of these elements of mensuration is so that braking measure is taked in ironmaking, significant to optimizing the blast furnace materials for this reason.
Smelt production requirement for satisfying, method of testing should have following features: (1) analyte item kind is complete, can both measure the material of the smelting processes such as iron ore, dedusting ash, mud, coke, coal dust, slag specimen; (2) the analysis content range is wide, can be used for the mensuration that content is 0.00X-X.XX%, and wherein the measurement range upper limit of zinc element can reach 35%; (3) simple to operate, be easy to grasp.
When at present the assorted material of metallurgy such as iron ore etc. being processed, a kind of is to adopt fusion method, but the elements to be measured such as introducing sodium element that this method can be extra; A kind of is that used acid is generally the acid mixture of hydrochloric acid and nitric acid with the acid dissolving, but adopts this acid mixture not to be suitable for the assorted material of various metallurgy, and the solution of gained all presents muddy state after the sample dissolution.
Traditional photometry complex steps, operating conditions is restive, and reagent consumption is large; Atomic absorption spectrography (AAS) is fairly simple, but because measurement range is narrower, and can only carry out single element and measure, be difficult to satisfy the requirement of large Lot sample multielement analysis.Although X-fluorescence is simple and efficient, be subject to matrix effect, be only suitable for the single variety of similar matrix, and need complete standard substance to set up curve.
Summary of the invention
Determination method when multiple element is provided provide for the defective of above-mentioned existence in the assorted material of a kind of metallurgy, this while assay method is by selecting suitable sample treatment, mate neatly matrix, reasonably optimize instrument parameter, guaranteed the Accurate Determining of multiple element in the metallurgical assorted material of different cultivars wide region.
Technical scheme of the present invention is: determination method when multiple element in the assorted material of a kind of metallurgy, may further comprise the steps: the processing of (1) sample: take by weighing sample, at first use the acid mixture that is formed by hydrochloric acid, hydrofluorite and perchloric acid that sample is dissolved fully, obtain sample solution; Then heat the evaporate to dryness sample solution, add again repeatedly evaporate to dryness three times of redistilled water, residual acid mixture is removed fully; Use at last 5ml hydrochloric acid constant volume in the 100ml volumetric flask, obtain sample, stand-by;
(2) drafting of working curve: at first select knownly to contain trace element to be measured or do not contain the similar or identical standard substance of the type of element to be measured as base matter, then according to step (1) base matter is processed and constant volume in the 100ml volumetric flask; Add at last the element mixed standard solution to be measured of variable concentrations gradient, draw out working curve with this;
(3) mensuration of sample: the content of the sample of step (1) gained being measured multiple element to be measured in the sample with inductive coupling plasma emission spectrograph.
When carrying out the mensuration of step (3) sample, the condition determination of described inductive coupling plasma emission spectrograph is: the radio-frequency generator operating power is 1400W, and cooling gas flow is 12L/min, and the atomization gas flow is 1.0L/min, the assisted gas flow is 0.8L/min, flush time 45s.
Described sample is iron ore or dedusting ash or mud or coal dust or the slag specimen in the metallurgical assorted material.
Described acid mixture is comprised of 5ml hydrochloric acid, 2ml hydrofluorite and 3ml perchloric acid.
Beneficial effect of the present invention is: while assay method of the present invention, and adopt the acid mixture that is formed by hydrochloric acid, hydrofluorite and perchloric acid that sample is dissolved, it is pure that the hydrochloric acid in the acid mixture, hydrofluorite and perchloric acid are top grade.This acid mixture utilizes the strong oxidizing property of perchloric acid and the strong complexing dissolving power of hydrofluorite and hydrochloric acid, can make the assorted material of various metallurgy sample dissolution complete, and gained solution is limpid.Use this acid mixture so that the scope of application of metallurgical assorted material sample is more extensive, can be used for the assorted material of the multiple metallurgy such as iron ore, dedusting ash, mud, coke, coal dust, slag specimen.
In order to guarantee the stability of Specimen Determination, must guarantee the acid mixture of noresidue in the sample, owing to having added perchloric acid in the acid mixture, not only can utilize the strong oxidizing property of perchloric acid, when heating evaporate to dryness sample solution, because perchloric acid is active, be easy to decompose volatilization simultaneously, hydrochloric acid and hydrofluorite can be taken out of, accelerate the removal of acid mixture.Then add again repeatedly evaporate to dryness three times of redistilled water, can remove up hill and dale residual acid mixture, both guaranteed the stability of sample, can prevent that again the remaining hydrogen fluoric acid from producing corrosion to the quartz ampoule in the testing tool.
In order to ensure measuring when multiple element in the assorted material of metallurgy, especially in the situation that there is not the series standard material, must mate flexibly matrix, reasonably the drawing curve.The present invention selects knownly to contain trace element to be measured or do not contain the similar or identical standard substance of the type of element to be measured as base matter, adds the element mixed standard solution to be measured of variable concentrations gradient, with this drawing curve, can eliminate the interference of matrix.
In the assorted material of metallurgy of the present invention when multiple element determination method possess following advantage: (1) has remedied the deficiency in Atomic absorption, the xrf analysis method, expanded the coverage of analyzing kind, compare with manual chemical method, easy, quick, environmental protection, be easy to grasp, have higher accuracy and precision preferably.(2) check on and instruct ironmaking production and scientific research public relations to play an important role for advancing factory's raw material, in iron-making production, according to analyzing data adjustment batching, promote the raising of product quality, reduce waste product, create beneficial result.
Embodiment
Optimizing instrument parameter is to satisfy the necessary condition of analytical test, and just details are as follows for the optimization reason of Instrumental parameter of the present invention:
1, the selection of analysis spectral line
Selection for analysis spectral line, usually according to the interference element that exists in the height of constituent content to be measured and the sample, the clean intensity of selection emission is large, signal-to-background ratio is high, coexistence elements disturb few spectral line as element analysis spectrum line to be measured, this experiment is comprehensively compared by each is measured many spectral lines of element, and each element optimized analysis spectral line of selection sees Table 1.
The selection of table 1. analysis spectral line
2, the selection of high frequency power
Alkali metal is after ionization, its exoelectron structure has just had the rock-steady structure of inert gas, therefore to make again it just excite in the extreme difficulty, alkali metal element K, Na very easily ionizes, the excitation energy that needs is very low, and the Pb of difficult ionization, the elements such as As need higher excitation energy, the height of power directly affects the height at plasmatorch exposure position, when the exposure position is too low, signal weaker, and the excitation energy of ICP is crossed the high ionization serious interference, can not obtain desirable clean intensity level, investigate different capacity to the impact of each element spectral line intensity, consider the detection limit of each element and the increase of output power to the quarter bend impact in serviceable life, this method is selected high frequency power 1400W.
3, the selection of atomization gas flow
The atomization gas flow is one of key factor that affects signal intensity, the size of atomization gas flow directly affects the atomizer lifting capacity, nebulization efficiency, droplet grain hydrocarbon, the residence time of gasoloid in passage etc., increase the atomization gas flow and can improve nebulization efficiency, lifting capacity increases, but the too high meeting of atomization gas flow has influence on the stability of plasma, found through experiments, the sodium element of atomization gas flow commute ionization and the lead of difficult ionization, the arsenic impact is larger, to potassium, zinc, the impact of the elements such as copper is less, when the atomization gas flow surpasses 1.1L/min, plasma flame is unstable, when the atomization gas flow is lower than, intensity plumbous and arsenic obviously descends, and considers the impact on each element, selects atomization gas flow 1.0L/min.
4, the selection of assisted gas flow
Assisted gas is the air-flow in the middle of the quarter bend, is used for lighting plasma and protection quarter bend.For most of elements to be measured (except Cd); the assisted gas flow is also not obvious on the impact of line strength; increase along with the assisted gas flow; each element spectral line intensity to be measured all has a declining tendency; the assisted gas flow is 1.0 when above, and line strength descends comparatively obvious, slows down to downtrending in 0.8 o'clock; consider assisted gas to the protective effect of quarter bend, select assisted gas flow 0.8L/min.
5, the selection of flush time
When the mensuration trace element, easily be subjected to the impact of memory effect, must guarantee enough flush times, especially when the sample that mensuration content fluctuates larger, if flush time is not enough, the data precision of collection is obviously bad, and this method is selected flush time 45 seconds.
The below describes the present invention take iron ore as sample:
(1) processing of sample: take by weighing iron ore sample 0.1g and place the platinum ware, at first use the acid mixture that is formed by 5ml hydrochloric acid, 2ml hydrofluorite and 3ml perchloric acid that sample is dissolved fully, obtain sample solution; Then heat the evaporate to dryness sample solution, add repeatedly evaporate to dryness three times of redistilled water again, occur without white cigarette when treating to heat evaporate to dryness for the third time, this moment, residual acid mixture was removed fully, and the amount that at every turn adds redistilled water is 5ml; Use at last 5ml hydrochloric acid constant volume in the 100ml volumetric flask, regulate acidity 5%, obtain sample, stand-by.In the sample preparation process, must guarantee that agents useful for same can not introduce the impurity such as element to be measured; And guarantee acid mixture removing residual in the sample fully.
(2) drafting of working curve: claim 6 parts of same standards for iron ore sample 0.1g that do not contain element to be measured, then according to step (1) base matter is processed and constant volume in the 100ml volumetric flask; The element mixed standard solution to be measured that adds respectively at last variable concentrations is with this drawing curve;
(3) mensuration of sample: the content of the sample of step (1) gained being measured multiple element to be measured in the sample with inductive coupling plasma emission spectrograph, wherein condition determination is: the radio-frequency generator operating power is 1400W, cooling gas flow is 12L/min, the atomization gas flow is 1.0L/min, the assisted gas flow is 0.8L/min, flush time 45s.
According to the method described above Bei Gangyuan production is numbered the GSBH30001-97 standard substance and tests, collect three day data, measure every day three times, the results are shown in following table 2.
Table 2. method precision and accuracy experimental data (%)
According to implementation method the standard substance of the known constituent content to be measured of portion is added a certain amount of element to be measured, the test recovery the results are shown in Table 3.
Table 3. recovery testu data (%)
Test data after upper enforcement can find out, all in work tolerance scope, the recovery of each element has been verified the accuracy of method to this method measured value between 96%～105%.
Dedusting ash, mud, coke, coal dust be because wherein fixed carbon content is high in the assorted material of metallurgy, needs to measure to remove the impurity element in the ash content behind the fixed carbon, and iron ore and slag specimen can directly be measured.The present invention can measure simultaneously to multiple elements such as potassium, sodium, lead, zinc, arsenic, copper.
It is pure that the hydrochloric acid that adopts in the acid mixture of the present invention, hydrofluorite and perchloric acid are top grade, adopts pure hydrochloric acid, hydrofluorite and the perchloric acid of top grade can be used for improving dissolved efficiency.The hydrochloric acid that is used for constant volume also is that top grade is pure.
Claims (4)
1. determination method when multiple element in the assorted material of a metallurgy may further comprise the steps:
(1) processing of sample: take by weighing sample, at first use the acid mixture that is formed by hydrochloric acid, hydrofluorite and perchloric acid that sample is dissolved fully, obtain sample solution; Then heat the evaporate to dryness sample solution, add again repeatedly evaporate to dryness three times of redistilled water, residual acid mixture is removed fully; Use at last 5ml hydrochloric acid constant volume in the 100ml volumetric flask, obtain sample, stand-by;
(2) drafting of working curve: at first select knownly to contain trace element to be measured or do not contain the similar or identical standard substance of the type of element to be measured as base matter, then according to step (1) base matter is processed and constant volume in the 100ml volumetric flask; Add at last the element mixed standard solution to be measured of variable concentrations gradient, draw out working curve;
(3) mensuration of sample: the content of the sample of step (1) gained being measured multiple element to be measured in the sample with inductive coupling plasma emission spectrograph.
2. determination method when multiple element in the assorted material of metallurgy according to claim 1 is characterized in that, is carrying out step (3)
During the mensuration of sample, the condition determination of described inductive coupling plasma emission spectrograph is: the radio-frequency generator operating power is
1400W, cooling gas flow are 12L/min, and the atomization gas flow is 1.0L/min, and the assisted gas flow is 0.8L/min, flush time 45s.
3. determination method when multiple element in the assorted material of metallurgy according to claim 1 is characterized in that, described sample be metallurgical assorted iron ore or dedusting ash or mud or coke or coal dust or slag specimen in expecting.
4. determination method when multiple element in the assorted material of metallurgy according to claim 1 is characterized in that, described acid mixture is comprised of 5ml hydrochloric acid, 2ml hydrofluorite and 3ml perchloric acid.
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Cited By (6)
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| CN103411989A (en) * | 2013-07-30 | 2013-11-27 | 山西太钢不锈钢股份有限公司 | Analytical method for fly ash in blast furnace |
| CN104897647A (en) * | 2015-06-26 | 2015-09-09 | 山东钢铁股份有限公司 | Method for measuring contents of potassium, sodium, lead, zinc, arsenic and copper in ferrous metallurgy materials |
| CN106706533A (en) * | 2016-12-30 | 2017-05-24 | 杭州谱育科技发展有限公司 | Sample intelligent analysis method |
| CN107561061A (en) * | 2017-08-23 | 2018-01-09 | 包头钢铁（集团）有限责任公司 | The assay method of potassium sodium Pb, Zn content in a kind of iron ore |
| CN108627374A (en) * | 2018-04-25 | 2018-10-09 | 山西建龙实业有限公司 | The assay method of Zn content in a kind of iron ore |
| CN109612795A (en) * | 2018-12-12 | 2019-04-12 | 云南锡业矿冶检测中心有限公司 | Impurities analysis detection method in a kind of tin and tin alloy |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103411989A (en) * | 2013-07-30 | 2013-11-27 | 山西太钢不锈钢股份有限公司 | Analytical method for fly ash in blast furnace |
| CN104897647A (en) * | 2015-06-26 | 2015-09-09 | 山东钢铁股份有限公司 | Method for measuring contents of potassium, sodium, lead, zinc, arsenic and copper in ferrous metallurgy materials |
| CN106706533A (en) * | 2016-12-30 | 2017-05-24 | 杭州谱育科技发展有限公司 | Sample intelligent analysis method |
| CN106706533B (en) * | 2016-12-30 | 2019-11-01 | 杭州谱育科技发展有限公司 | Sample intelligent analysis method |
| CN107561061A (en) * | 2017-08-23 | 2018-01-09 | 包头钢铁（集团）有限责任公司 | The assay method of potassium sodium Pb, Zn content in a kind of iron ore |
| CN108627374A (en) * | 2018-04-25 | 2018-10-09 | 山西建龙实业有限公司 | The assay method of Zn content in a kind of iron ore |
| CN109612795A (en) * | 2018-12-12 | 2019-04-12 | 云南锡业矿冶检测中心有限公司 | Impurities analysis detection method in a kind of tin and tin alloy |
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Application publication date: 20130403 |