阅读说明：本技术 一种测定艾萨熔炼炉炉渣中元素含量的方法 (Method for measuring content of elements in slag of pizza smelting furnace ) 是由 赵荣龙 何正华 杨世莹 刘金龙 朱子贤 苏为强 杨旺 蔡孟瑶 罗国清 宋纲 于 2021-02-10 设计创作，主要内容包括：本发明公开了一种测定艾萨熔炼炉炉渣中元素含量的方法。所述测定艾萨熔炼炉炉渣中元素含量的方法包括：制备待测样片、标准样片；采用X射线荧光光谱仪测定标准样片中待测元素的荧光强度,并根据所述标准样片中待测元素的荧光强度与所述标准值绘制得到无校正的标准曲线；采用理论α系数或谱线干扰重叠校正法对无校正的标准曲线进行校正,得到标准曲线；采用X射线荧光光谱仪测定待测样片中待测元素的荧光强度,根据标准曲线和所述待测样片中待测元素的荧光强度得到待测艾萨熔炼炉炉渣中待测元素含量。与传统的化学分析法相比,本发明所述的测定艾萨熔炼炉炉渣中元素含量的方法具有操作简单,流程短,精确度高的特点。(The invention discloses a method for measuring the content of elements in slag of an pizza smelting furnace. The method for measuring the content of elements in the slag of the pizza smelting furnace comprises the following steps: preparing a sample wafer to be tested and a standard sample wafer; measuring the fluorescence intensity of the element to be measured in the standard sample by using an X-ray fluorescence spectrometer, and drawing a standard curve without correction according to the fluorescence intensity of the element to be measured in the standard sample and the standard value; correcting the standard curve without correction by adopting a theoretical alpha coefficient or spectral line interference overlapping correction method to obtain a standard curve; and measuring the fluorescence intensity of the element to be measured in the sample to be measured by adopting an X-ray fluorescence spectrometer, and obtaining the content of the element to be measured in the slag of the pizza smelting furnace to be measured according to the standard curve and the fluorescence intensity of the element to be measured in the sample to be measured. Compared with the traditional chemical analysis method, the method for measuring the content of the elements in the slag of the pizza smelting furnace has the characteristics of simple operation, short flow and high accuracy.)

1. A method for measuring the content of elements in slag of an pizza smelting furnace is characterized by comprising the following steps:

preparing the slag of the pizza smelting furnace to be tested by adopting a sample preparation method to obtain a sample to be tested;

the method comprises the steps of measuring standard values of the content of elements to be measured in the slag of a plurality of standard pizza smelting furnaces in advance, and preparing the slag of the plurality of standard pizza smelting furnaces into a plurality of standard sample wafers by a sample wafer preparation method;

preparing the slag of the pizza smelting furnace for instrument drift correction by adopting a sample preparation method to obtain an instrument drift correction sample;

performing instrument drift correction on the X-ray fluorescence spectrometer by adopting an instrument drift correction sample, measuring the fluorescence intensity of the element to be measured in each standard sample by adopting the X-ray fluorescence spectrometer, and drawing a standard curve without correction according to the fluorescence intensity of the element to be measured in each standard sample and the standard value; correcting the standard curve without correction by adopting a theoretical alpha coefficient or spectral line interference overlapping correction method to obtain a standard curve;

and performing instrument drift correction on the X-ray fluorescence spectrometer by adopting an instrument drift correction sample wafer, measuring the fluorescence intensity of the element to be measured in the sample wafer to be measured by adopting the X-ray fluorescence spectrometer, and obtaining the content of the element to be measured in the slag of the pizza smelting furnace to be measured according to the standard curve and the fluorescence intensity of the element to be measured in the sample wafer to be measured.

2. The method for determining the content of elements in the slag of the pizza smelting furnace according to claim 1, wherein the elements to be measured comprise: one or more of S, Fe, As, Sb, Bi, Pb, Zn, Ni, Cu, Ca, Mg, Al and Si.

3. The method for determining the content of elements in the slag of the pizza smelting furnace according to claim 1, wherein the preparation method of the sample comprises: powder tabletting method and glass melt-extrusion method.

4. The method of determining the elemental content of pizza smelting furnace slag according to claim 3, wherein the powder slugging method comprises:

and scooping the sample with a sample spoon, placing the sample in a sample pressing ring of a sample pressing machine, adjusting the pressure of the sample pressing machine, and pressing to obtain a sample wafer.

5. The method of determining the elemental content of pizza smelter slag according to claim 3, characterized in that the glass-fritting method comprises:

mixing the mixed solvent, the release agent and the sample in a platinum crucible, melting, and demoulding to prepare a sample wafer.

6. The method of determining the elemental content of pizza smelting furnace slag according to claim 5, wherein the mixed solvent comprises: one or two of anhydrous lithium tetraborate and lithium metaborate.

7. The method of determining elemental content in pizza smelting furnace slag according to claim 5, wherein the mold release agent comprises: one or more of ammonium iodide and lithium iodide.

8. The method of determining the elemental content of pizza smelting furnace slag according to claim 5, characterized in that the melting temperature is 1050-1100 ℃.

9. The method of determining the elemental content of pizza smelting furnace slag according to claim 1, wherein the number of said standard coupons is at least 5.

10. The method for determining the content of elements in the slag of the pizza smelting furnace according to claim 1, further comprising, after the obtaining the standard curve, accepting the standard curve;

the acceptance of the standard curve comprises:

determining a standard value of the content of the element to be detected in the slag of the pizza smelting furnace for acceptance;

preparing slag of an pizza smelting furnace for acceptance inspection into an acceptance inspection standard sample;

performing instrument drift correction on the X-ray fluorescence spectrometer by adopting an instrument drift correction sample, measuring the fluorescence intensity of the acceptance standard sample by adopting the X-ray fluorescence spectrometer, and determining to obtain a measured value according to the standard curve and the measured fluorescence intensity of the acceptance standard sample;

and comparing the measured value with the standard value, and judging whether the obtained standard curve meets the acceptance standard.

Technical Field

The invention relates to the field of element analysis, in particular to a method for measuring the content of elements in slag of an pizza smelting furnace.

Background

Currently, about 80% of the copper in the world is produced by pyrometallurgy. Thus, pyrometallurgical copper is dominant.

The slag of the Isa smelting furnace refers to copper-containing slag produced by the Isa pyrometallurgy, and contains various elements such as copper, iron, sulfur, silicon dioxide, arsenic, lead, zinc, antimony, bismuth, nickel, calcium oxide, magnesium oxide, aluminum oxide and the like. The slag of the pizza smelting furnace produced by the southwest copper division of the Yunan copper share is high in impurity content and complex and variable in components, and the change of the components has important influence on the properties of the furnace. Such as: silicon to iron ratio (SiO)₂Fe) is an important parameter for the properties of copper metallurgical slags. FeO can reduce the viscosity, improve the fluidity, and lower the melting point, but increases the specific gravity of the slag and the amount of the slag, and reduces the activity coefficient of CuO. A certain content of SiO in the slag₂Can ensure good separation of slag and copper matte. Therefore, the rapid and accurate component analysis data is particularly important for the component control of the slag of the Isa furnace and the smelting production of copper.

No standard analysis method exists for analyzing and detecting the components of the slag of the Isa smelting furnace, and partial element measurement can be carried out by referring to GB/T3884 copper concentrate chemical analysis method, but the method relates to a volumetric method, an atomic absorption spectrometry, an ICP-AES method and the like. The analysis methods have long flows, cannot meet the requirement of rapid analysis in production, and also need to use a large amount of toxic chemical reagents, which can cause harm to the environment and the occupational health of operators.

Accordingly, the prior art is yet to be improved and developed.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a method for measuring the content of elements in the slag of an pizza smelting furnace, and aims to solve the problem that the existing analytical method of the slag of the pizza smelting furnace needs to use a large amount of toxic and harmful chemical reagents and causes harm to the environment and the occupational health of operators.

A method for measuring the content of elements in slag of an pizza smelting furnace comprises the following steps:

preparing a sample wafer to be tested from the slag of the pizza smelting furnace to be tested by a sample wafer preparation method;

the method comprises the steps of measuring a standard value of the content of an element to be measured in standard pizza smelting furnace slag in advance, and preparing a standard sample from the standard pizza smelting furnace slag by a sample preparation method;

preparing an instrument drift correction sample wafer from the slag of the pizza smelting furnace for instrument drift correction by adopting a sample wafer preparation method;

performing instrument drift correction on the X-ray fluorescence spectrometer by using an instrument drift correction sample wafer, measuring the fluorescence intensity of an element to be measured in a standard sample wafer by using the X-ray fluorescence spectrometer, and drawing a standard curve without correction according to the fluorescence intensity of the element to be measured in the standard sample wafer and the standard value;

correcting the standard curve without correction by adopting a theoretical alpha coefficient or spectral line interference overlapping correction method to obtain a standard curve;

and performing instrument drift correction on the X-ray fluorescence spectrometer by adopting an instrument drift correction sample wafer, measuring the fluorescence intensity of the element to be measured in the sample wafer to be measured by adopting the X-ray fluorescence spectrometer, and obtaining the content of the element to be measured in the slag of the pizza smelting furnace to be measured according to the standard curve and the fluorescence intensity of the element to be measured in the sample wafer to be measured.

The method for measuring the content of the elements in the slag of the pizza smelting furnace comprises the following steps: one or more of S, Fe, As, Sb, Bi, Pb, Zn, Ni, Cu, Ca, Mg, Al and Si.

The method for measuring the content of elements in the slag of the pizza smelting furnace comprises the following steps: powder tabletting method and glass melt-extrusion method.

The method for measuring the content of elements in the slag of the pizza smelting furnace comprises the following steps:

and scooping the sample with a sample spoon, placing the sample in a sample pressing ring of a sample pressing machine, adjusting the pressure of the sample pressing machine, and pressing to obtain a sample wafer.

The method for measuring the content of elements in the slag of the pizza smelting furnace comprises the following steps:

mixing the mixed solvent, the release agent and the sample in a platinum crucible, melting, and demoulding to prepare a sample wafer.

The method for measuring the content of elements in the slag of the pizza smelting furnace comprises the following steps: one or two of anhydrous lithium tetraborate and lithium metaborate.

The method for measuring the content of elements in the slag of the pizza smelting furnace comprises the following steps: one or more of ammonium iodide and lithium iodide.

The method for measuring the content of elements in the slag of the pizza smelting furnace is characterized in that the melting temperature is 1050-1100 ℃.

The method for measuring the content of elements in the slag of the pizza smelting furnace is characterized in that the number of the standard sample pieces is at least 5.

The method for measuring the content of the elements in the slag of the pizza smelting furnace comprises the following steps of obtaining a standard curve, and checking and accepting the standard curve;

the acceptance of the standard curve comprises:

determining a standard value of the content of the element to be detected in the slag of the pizza smelting furnace for acceptance;

preparing slag of an pizza smelting furnace for acceptance inspection into an acceptance inspection standard sample;

performing instrument drift correction on the X-ray fluorescence spectrometer by adopting an instrument drift correction sample, measuring the fluorescence intensity of the acceptance standard sample by adopting the X-ray fluorescence spectrometer, and obtaining a measured value according to the standard curve and the measured fluorescence intensity of the acceptance standard sample;

and comparing the measured value with the standard value, and judging whether the obtained standard curve meets the acceptance standard.

Has the advantages that: compared with the traditional chemical analysis method, the method for measuring the content of the elements in the slag of the pizza smelting furnace has the characteristics of simple operation, short flow and high accuracy.

Drawings

FIG. 1 is a graph showing a calibration standard curve of copper element in example 1 of the present invention;

FIG. 2 is a graph showing a standard curve of copper element in example 1 of the present invention;

FIG. 3 is a graph showing a calibration standard curve of Fe element in example 1 of the present invention;

FIG. 4 is a graph showing a standard curve of an iron element in example 1 of the present invention;

FIG. 5 is a graph showing the calibration standard curve of elemental calcium oxide in example 1 of the present invention;

FIG. 6 is a graph showing a standard curve of calcium oxide in example 1 of the present invention.

Detailed Description

The invention provides a method for measuring the content of elements in slag of an pizza smelting furnace, and the invention is further described in detail below in order to make the purpose, the technical scheme and the effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the nonferrous metallurgy, steel and cement industries, the X-ray fluorescence spectrometry (XRF) is adopted to analyze elements and the content of the elements, and the following defects exist:

1. although the tabletting analysis is fast, the analysis is influenced by the granularity effect, the mineral effect and the matrix effect of the sample, the linearity of the analysis curve is poor, and the accuracy is low.

2. The X-ray fluorescence spectrum analysis technology is not uniform, and the judgment is only carried out according to empirical values, such as the establishment of a uniform analysis curve acceptance standard and the related requirements on the drift correction coefficient of the analysis curve.

3. The one-step forming qualification rate of the glass fuse piece is low, and part of samples can meet the analysis requirement by carrying out secondary melting.

The invention provides a method for measuring the content of elements in slag of an pizza smelting furnace, which comprises the following steps:

s100, preparing a sample to be tested from the slag of the pizza smelting furnace to be tested by adopting a sample preparation method; the method comprises the steps of measuring a standard value of the content of an element to be measured in standard pizza smelting furnace slag in advance, and preparing a standard sample from the standard pizza smelting furnace slag by a sample preparation method; preparing an instrument drift correction sample wafer from the slag of the Isa smelting furnace for instrument drift correction by a sample wafer preparation method;

s200, performing instrument drift correction on the X-ray fluorescence spectrometer by using an instrument drift correction sample, measuring the fluorescence intensity of the element to be measured in the standard sample by using the X-ray fluorescence spectrometer, and drawing a standard curve without correction according to the fluorescence intensity of the element to be measured in the standard sample and the standard value;

s300, correcting the standard curve without correction by adopting a theoretical alpha coefficient or spectral line interference superposition correction method to obtain a standard curve;

s400, performing instrument drift correction on the X-ray fluorescence spectrometer by using an instrument drift correction sample, measuring the fluorescence intensity of the element to be measured in the sample to be measured by using the X-ray fluorescence spectrometer, and obtaining the content of the element to be measured in the slag of the pizza smelting furnace to be measured according to the standard curve and the fluorescence intensity of the element to be measured in the sample to be measured.

The method for measuring the content of elements in the slag of the pizza smelting furnace is a novel method for quickly detecting the components of the smelting slag in the smelting process of the pizza copper. The method for measuring the content of the elements in the slag of the pizza smelting furnace has short flow and high efficiency, can simultaneously carry out multi-element continuous measurement, and shortens the analysis time by more than 4 hours compared with a chemical analysis method. The invention has wide analysis element range, and can analyze more than 80 elements between Be (4) to U (92); the content range of the measured elements is wide, and the analysis can be carried out from 0.0001 percent to 100 percent. The method for measuring the content of the elements in the slag of the pizza smelting furnace has the characteristics of simplicity and time saving, can be applied to the control of the production process, and solves the defect that the traditional chemical method has inaccurate test.

The main purpose of the S100 is to prepare various samples for use. In one embodiment of the present invention, the sample preparation method includes: powder tabletting method and glass melt-extrusion method. Specifically, a sample to be detected is taken, and the sample is obtained through grinding, tabletting or melting. Wherein the sample wafer to be tested is a sample wafer containing the slag of the pizza smelting furnace to be tested. The standard sample is a sample containing standard pizza smelting furnace slag, wherein the standard pizza smelting furnace slag refers to that the content of elements (target elements) to be measured in the pizza smelting furnace slag is known, and the content can be specifically measured by a chemical analysis method. The instrument drift correction sample is a sample containing correction pizza smelting furnace slag and is used for instrument drift correction, and optionally, the content of the element to be measured in the correction pizza smelting furnace slag is known.

In one embodiment of the present invention, the element to be tested includes: one or more of S, Fe, As, Sb, Bi, Pb, Zn, Ni, Cu, Ca, Mg, Al and Si.

The chemical analysis method can be used for determining the content of the element to be detected by a chemical reagent by referring to a copper concentrate chemical analysis method.

In one embodiment of the present invention, the diameter of the sample wafer is in a range of 34mm to 45 mm. The diameter of the standard specimen piece was 36mm as described.

In one embodiment of the present invention, the powder tableting method comprises: and scooping the sample with a sample spoon, placing the sample in a sample pressing ring of a sample pressing machine, adjusting the pressure of the sample pressing machine, and pressing to obtain a sample wafer. Specifically, a sample pressing ring is placed in a sample pressing die, a sample spoon is used for scooping a proper amount of sample to be placed in the sample pressing ring, the pressure of a sample pressing machine is adjusted, and a sample wafer with a flat, smooth and crackless surface is pressed. Optionally, the pressing pressure is 40T-50T, and the holding time is 5 s-30 s.

In one embodiment of the present invention, the glass frit process comprises: and (3) properly mixing the mixed solvent, the release agent and the sample in a platinum crucible, melting, and demolding to prepare a sample wafer. Specifically, a certain amount of mixed solvent, oxidant, mold release agent and sample are weighed and properly mixed in a platinum crucible, the sample is prevented from contacting the crucible wall and bottom, and a flat, smooth, crystal-free, crack-free and pore-free glass wafer (glass sample wafer) is prepared after pre-oxidation, melting and mold release. Optionally, the pre-oxidation temperature is 700 ℃ to 800 ℃, and the melting temperature is 1050 ℃ to 1100 ℃.

The invention can obtain flat, smooth, non-crystal, non-crack and non-bubble sample by using the technical parameters to prepare the sample, thereby meeting the requirement of rapid analysis. Moreover, the invention solves the problem of low one-step forming qualification rate of the existing glass fuse piece, and can realize the one-step forming qualification rate of more than 95 percent.

In one embodiment of the present invention, the mixed solvent is one or two of anhydrous lithium tetraborate and lithium metaborate; the release agent comprises: one or more of ammonium iodide and lithium iodide; the oxidant is one or more of ammonium nitrate and sodium nitrate. The invention adopts the mixed solvent to effectively eliminate the differences of granularity effect, mineral effect, nonuniformity and the like of the sample, and is more favorable for fast and accurately carrying out XRF and other analyses.

And S200, preparing a calibration-free standard curve through the standard sample. Wherein, before the standard sample is analyzed by the X-ray fluorescence spectrometer, instrument drift correction is needed. Specifically, the instrument drift correction is carried out on the instrument drift correction sample according to an operation program of the measuring instrument, and the correction times are 2 times. Optionally, the instrument drift correction comprises: s201, loading the instrument drift correction sample into an X-ray fluorescence spectrometer, and testing the fluorescence intensity of the detected element, wherein the fluorescence intensity is used as the basis of the drift correction of the X-ray fluorescence spectrometer; s202, the instrument drift correction sample is loaded into an X-ray fluorescence spectrometer, and the X-ray fluorescence spectrometer is corrected, so that the fluorescence intensity of the detected element in the instrument drift correction obtained by detection at the moment is consistent with the fluorescence intensity of the element detected in the S201.

In one embodiment of the invention, the content of elements in the pizza smelting furnace slag instrument drift correction sample is not less than 0.01%. The drift correction factor should be between 0.95 and 1.05. The technical parameters are set to ensure the accuracy of the analysis and detection result.

In one embodiment of the invention, the number of standards is at least 5. Optionally, the standard sample wafer should use at least 5 different types of standard samples and can cover the content range of the measured elements. That is, the contents of the detected elements in the standard sample are different, and the two end value ranges of the detected elements cover the contents of the detected elements in the sample to be detected. Furthermore, the content of the element to be measured in the plurality of standard sample wafers is uniformly distributed in the range of the two end values.

In the S200, including: s203, inputting chemical method fixed values of the standard sample according to an operation program of the X-ray measuring spectrometer, and sequentially measuring the X-ray fluorescence intensity of the elements to be measured in each standard sample; and the X-ray spectrometer performs regression analysis by using a calculation formula according to the measured fluorescence intensity of each element in each standard sample and the standard value measured by a chemical method, and draws a calibration-free standard curve. The working conditions of the X-ray fluorescence spectrometer corresponding to the detected elements are shown in Table 1.

TABLE 1 working conditions of X-ray fluorescence spectrometer

Element(s)

S

Fe

As

Sb

Bi

Pb

Zn

Ni

Cu

Ca

Mg

Al

Si

Analyzing crystals

Ge111

LiF200

LiF200

LiF200

LiF200

LiF200

LiF200

LiF200

LiF200

LiF200

PX1

PE002

PE002

Analysis line

Ka

Ka

Kβ

Ka

Lβ

Lβ

Kβ

Ka

Ka

Ka

Ka

Ka

Ka

Collimator

300μm

300μm

300μm

300μm

300μm

300μm

300μm

300μm

300μm

300μm

700μm

300μm

300μm

Detector

Flow

Flow

scint

scint

scint

scint

scint

scint

Flow

Flow

Flow

Flow

Flow

Optical filter

None

Al(200μm)

None

None

None

None

None

None

None

None

None

None

None

Current voltage

30/100

60/50

60/50

60/50

60/50

60/50

60/50

60/50

60/50

30/100

30/100

30/100

30/100

In S300, the measurement value is calibrated in consideration of the influence of the difference between the coexisting elements and the matrix, and a standard curve is obtained. The calibration method can select theoretical alpha coefficient, spectral line interference overlap correction and other methods. The theoretical alpha coefficient method is used for theoretically calculating the absorption and enhancement effects of the matrix and enhancing the absorption effects among the form elements of the alpha coefficient. In an embodiment of the present invention, the correction factor in S300 should be less than 5, so as to ensure the accuracy of the result.

In an embodiment of the present invention, after the obtaining of the standard curve, the acceptance of the standard curve is further included. Specifically, one or more acceptance standard sample sheets are selected, wherein the content of the measured element in the acceptance standard sample sheets is known, and optionally, the standard value of the content of the measured element in the acceptance standard sample sheets is determined by a chemical analysis method; and (4) measuring the content of the element to be measured in the acceptance standard sample by adopting an X-ray spectrometer, comparing the content with a standard value, and judging whether the obtained standard curve meets the requirement.

In the process of checking and accepting the standard curve, the accuracy of each element of the analysis line is verified by adopting a sample with a credible reference value, and whether the obtained standard curve meets the requirements or not is judged. The absolute value of the relative deviation between the measured value and the standard value of the measured element satisfies the following table 2:

TABLE 2 relative deviation requirement of measured values and standard values of the elements to be measured

Therefore, the invention provides a method and a standard for analyzing the acceptance of the curve, solves the technical problem and realizes the effective monitoring of the standard curve drift.

In one embodiment of the present invention, the acceptance of the standard curve comprises: obtaining a standard value of the content of the element to be detected from the slag of the pizza smelting furnace for acceptance inspection by a chemical analysis method; preparing slag of an pizza smelting furnace for acceptance inspection into an acceptance inspection standard sample; performing instrument drift correction on the X-ray fluorescence spectrometer by adopting an instrument drift correction sample, measuring the fluorescence intensity of the element to be measured in the acceptance standard sample by adopting the X-ray fluorescence spectrometer, and obtaining a measured value according to the standard curve and the measured fluorescence intensity of the acceptance standard sample; and comparing the measured value with the standard value, and judging whether the obtained standard curve meets the acceptance standard. Optionally, the content of the measured element in the acceptance standard sample is different from the content of the measured element in the standard sample.

In the step S400, the instrument drift correction is carried out on the X-ray fluorescence spectrometer by adopting the instrument drift correction sample wafer, the standard sample wafer is subjected to fluorescence analysis on the X-ray fluorescence spectrometer to obtain the fluorescence intensity of the element to be detected, the X-ray fluorescence intensity of the element to be detected is brought into a corresponding standard curve by the X-ray fluorescence spectrometer, and the percentage content of the element is automatically calculated.

The technical solution of the present invention will be described below by way of examples.

Example 1:

(1) in a prototype, melting the slag of the pizza smelting furnace to be analyzed and the mixed solvent for 8 minutes under shaking, adding about 0.3g of ammonium iodide, melting for 2 minutes again, starting cooling air to forcibly cool for 6 minutes, and taking out to obtain a sample wafer to be tested.

(2) In a prototype, 10 standard pizza smelting furnace slag and a mixed solvent are respectively melted for 8 minutes under shaking, about 0.3g of ammonium iodide is added, the mixture is melted for 2 minutes again, and the mixture is taken out after being forcibly cooled for 6 minutes by starting cooling air, so as to obtain 10 standard sample wafers; wherein the contents of the measured elements in the slag of the pizza smelting furnace corresponding to the 10 standard sample wafers are different, and the standard values are determined by a chemical analysis method.

(3) In a prototype, melting the slag of the Isa smelting furnace for correcting instrument drift and a mixed solvent for 8 minutes under shaking, adding about 0.3g of ammonium iodide, melting for 2 minutes again, starting cooling air to forcedly cool for 6 minutes, and taking out to obtain an instrument drift correction sample, wherein the content of the measured element in the slag of the Isa smelting furnace for correcting instrument drift is determined by a chemical fixed value method.

(5) Correcting the instrument drift of the instrument drift correction sample wafer according to an operation program of the measuring instrument, wherein the correction times are 2 times; respectively analyzing the 10 standard sample wafers by using an X-ray fluorescence spectrometer, measuring the fluorescence intensity of each element to be measured, establishing a regression equation between the fluorescence intensity of each element to be measured and the known content (standard value) of the element by using a regression analysis method, and drawing an uncorrected standard curve of each element in the standard melting slag sample.

(6) The influence of the difference between the coexisting elements and the matrix is taken into consideration, and the theoretical alpha coefficient is selected to correct the measured value, thereby obtaining a standard curve.

(7) Performing instrument drift correction on the instrument drift correction sample according to an operation program of the measuring instrument, wherein the correction times are 2 times; and analyzing the sample to be detected by adopting an X-ray fluorescence spectrometer, measuring the fluorescence intensity of various elements to be detected, and automatically calculating the percentage content of the elements according to the fact that the measured X-ray fluorescence intensity of the elements is brought into a corresponding standard curve.

The analysis conditions of the X-ray fluorescence spectrometer in this example are shown in Table 1.

In the step (2), the 10 standard sample pieces are domestic smelting slag standard samples and are standard sample pieces subjected to chemical law value setting.

In the steps (1) to (4), the mixed flux is a mixed flux of anhydrous lithium tetraborate and lithium metaborate, the ignition loss or the ignition increment is not more than 0.40%, the blank of calcium is not more than 0.3%, and the blank of aluminum is not more than 0.3%; wherein the anhydrous lithium tetraborate is 12g, and the lithium metaborate is 22 g; the platinum-gold crucible is Pt + Au (95% + 5% by mass).

In step (5), the calibration curves without correction of Cu, Fe, and CaO obtained by the above-described measurement method are shown in fig. 1, 3, and 5, respectively.

In the step (6), analysis curves after the theoretical alpha coefficient and the spectral line interference superposition correction are respectively shown in fig. 2, fig. 4 and fig. 6, wherein the abscissa is the mass percent of Cu, Fe and CaO in the standard melting slag sample, and the unit is%, and the ordinate is the fluorescence intensity measured by Cu, Fe and Ca elements, and the unit is kcps. The analysis range of the content of each element in the slag of the pizza smelting furnace to which the above measurement method is applied is shown in table 3.

TABLE 3 analysis range of contents of each element in the slag of the pizza smelting furnace

Element(s)	Mass fraction%	Element(s)	Mass fraction%
				Cu	0.50～20.00	Sb	0.05～0.20
Fe	25.00～45.00	Bi	0.005～0.10
				S	0.50～5.00	Ni	0.005～0.10
SiO2	20.00～45.00	CaO	0.50～4.00
				As	0.050～1.00	MgO	0.50～4.00
Pb	0.050～1.00	Al2O3	0.50～6.00
				Zn	0.050～4.00

And selecting a southwest copper industry pizza smelting furnace slag sample 0085 to compare the determination method with analytical results of a Kunming metallurgy research institute chemical method for feasibility evaluation. The comparison between the measured value of the primary and secondary element content in the standard sample T0085 and the chemical value by using the measuring method is shown in Table 4, and the repeatability test result of the primary and secondary element content measurement in the sample 0085 is shown in Table 5.

TABLE 4 comparison of measured values of the contents of major and minor elements in 0085 sample with standard values (%)

TABLE 5 repeatability test results (%)

From the experimental data in tables 4 and 5, the accuracy and precision of the method for measuring the contents of the primary and secondary elements in the slag of the pizza smelting furnace by using the X-ray spectrum fluorescence melting method meet the requirements of daily production, and the method has good feasibility.

In the step (7), a furnace slag sample 0259 of a southwest copper industry Isa smelting furnace with a chemical law value of Kunming metallurgy research institute is adopted to measure the content of primary and secondary elements. Firstly, a slag sample 0259 of the pizza smelting furnace is made into a slag 0259 sample of the pizza smelting furnace, and then an X-ray fluorescence spectrometer is adopted to measure the contents of primary and secondary elements in the sample. Table 6 shows the comparison of the values determined by the method described above for this sample with those determined by the chemical analysis method of Kunming Metallurgical research institute.

TABLE 6 comparison of the values determined for the primary and secondary element content in sample 0259 with the values determined by chemical analysis (%)

As can be seen from the data in Table 6, the method for determining the content of the elements in the slag of the pizza smelting furnace is simpler to operate and shorter in flow compared with the chemical analysis method, but the accuracy is comparable with the chemical analysis method, and the other side shows that the method has great application and popularization values.

Example 2:

the difference from the embodiment 1 is that the sample preparation method of the selected pizza smelting furnace slag sample to be measured, the standard sample and the instrument correction sample is a powder tabletting method, and other implementation steps are the same as the implementation example 1. The powder tabletting method comprises the following specific steps: firstly, selecting a proper sample pressing mold, placing a proper amount of sample in a PVC plastic sample pressing ring of a sample melting machine, starting a sample pressing machine to press, setting the pressure to be 50T, and keeping the pressure for 5 s. The thickness of the sample of the powder compressed tablet is 3mm, and the diameter is 34 mm. Table 7 shows the measured values of the contents of primary and secondary elements in the slag sample 0294 of the Issatchen smelting furnace in the southwest copper industry of this example, in comparison with the values measured by the chemical analysis method of Kunming metallurgy institute.

Table 7: the measured value of the content of the primary and secondary elements in the slag sample 0294 of the West copper industry pizza smelting furnace is compared with the measured value of the Kunming metallurgy institute chemical analysis method (%)

Example 3:

the difference from example 1 was that lithium iodide was selected as the release agent, and the amount of lithium iodide added was 0.025g, and the rest of the procedure was the same as in example 1. Table 8 shows the measured values of the contents of primary and secondary elements in slag sample 0333 of the pizza smelting furnace for the southwest cupper industry of this example, compared with the values measured by the chemical analysis method of kunming metallurgical institute.

TABLE 8 comparison of the values determined for the primary and secondary element content in the slag sample 0333 from the Issatchen smelting furnace, southwest, and the values determined by the Kunming Metallurgical institute chemical analysis (%)

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.