CN114965533A - Analysis method and sample preparation method of copper anode furnace slag - Google Patents
Analysis method and sample preparation method of copper anode furnace slag Download PDFInfo
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Abstract
The invention discloses an analysis method and a sample preparation method of copper anode furnace slag, wherein the analysis method comprises the following steps: providing a standard sample of copper anode furnace slag and a sample to be tested of the copper anode furnace slag; performing X-ray fluorescence spectrum analysis on the standard sample of the copper anode slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the standard sample of the copper anode slag; carrying out matrix effect correction on each detection element of the standard sample of the copper anode slag, and drawing a standard analysis working curve of each detection element of the copper anode slag; performing X-ray fluorescence spectrum analysis on the copper anode slag to-be-detected sample by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the copper anode slag to-be-detected sample; and obtaining the content of each detection element according to the fluorescence intensity of each detection element of the copper anode furnace slag sample to be detected and a standard analysis working curve. The analysis method has the advantages of high detection accuracy, high analysis speed, wide element analysis range, high safety coefficient and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of copper anode slag detection, in particular to an analysis method and a sample preparation method of copper anode slag.
Background
At present, the copper smelting capacity of China is about 500 million t/year, the total amount of the copper smelting capacity of the world is about 2000 million t/year, and 90 percent of the capacity is obtained by pyrometallurgical smelting. The copper anode furnace is important equipment for fire refining, and is used for extracting crude copper or scrap copper with higher purity into anode copper, and then casting the liquid anode copper into a copper anode plate through casting equipment so as to provide a production raw material for copper electrolysis. The copper anode slag is a melt floating on the surface of an anode copper liquid generated in the process of refining anode copper by a copper anode furnace pyrogenic process, and the chemical composition of the copper anode slag is mainly copper oxide, cuprous oxide, a copper simple substance, aluminum oxide, magnesium oxide, silicon dioxide, complex oxides formed by nickel, magnesium, iron and silicon, and the like. The copper anode furnace slag plays a decisive role in ensuring the smooth operation of the smelting process, the quality of anode copper, the metal recovery rate and the like. The accurate analysis of the main chemical contents of the copper anode furnace slag not only meets the requirements of the production process, but also meets the requirements of environmental protection and comprehensive recycling of smelting solid wastes. At present, the most common analysis method for the contents of main chemical compositions in copper anode furnace slag, such as copper, iron and silicon dioxide, is a chemical wet method, although the classical analysis methods have high accuracy and good precision, because all components can not be measured simultaneously, the wet method is required to be repeated according to the method of each element to dissolve a sample, the operation procedure is complicated, the analysis period is long, and various dangerous chemicals, such as hydrochloric acid, nitric acid, sulfuric acid and the like, are required to be used to dissolve the sample, so that the physical health of an analyst is damaged, and the environment is polluted. Meanwhile, trace elements such as antimony, bismuth, nickel, lead and the like in the copper anode furnace slag need to be measured by inductively coupled plasma atomic emission spectroscopy or atomic absorption spectroscopy, and the methods still do not get rid of the complicated process of dissolving samples by a chemical wet method. Therefore, a great deal of labor and time is required to complete the analysis of all the main constituent elements of a copper anode slag sample.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide an analysis method and a sample preparation method for copper anode slag, which aims to solve the problem that a great deal of manpower and time are required to be invested in the prior art for completely analyzing all main constituent elements of a copper anode slag sample.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an analysis method of copper anode slag comprises the following steps:
providing a standard sample of copper anode furnace slag and a sample to be tested of the copper anode furnace slag;
performing X-ray fluorescence spectrum analysis on the standard sample of the copper anode slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the standard sample of the copper anode slag;
carrying out matrix effect correction on each detection element of the standard sample of the copper anode furnace slag, and drawing a standard analysis working curve of each detection element of the copper anode furnace slag;
performing X-ray fluorescence spectrum analysis on the copper anode slag to-be-detected sample by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the copper anode slag to-be-detected sample;
and obtaining the content of each detection element of the copper anode furnace slag to-be-detected sample according to the fluorescence intensity of each detection element of the copper anode furnace slag to-be-detected sample and the standard analysis working curve of each detection element of the copper anode furnace slag.
The analysis method of the copper anode furnace slag comprises the following steps of: cu, Fe, Ni, As, Pb, Zn, Sb, Bi, Al 2 O 3 、SiO 2 、MgO、CaO。
The analysis method of the copper anode furnace slag comprises the following steps of carrying out analysis on the copper anode furnace slag, wherein the standard sample of the copper anode furnace slag is the copper anode furnace slag of the production process with gradient detection element content from low to high.
The analysis method of the copper anode furnace slag comprises the following steps of
Wherein C is i As the concentration of the element to be measured, D i To correct for background values, I i As intensity of the element to be measured, k 0 、k ij To correct the coefficients, I j The strength of the matrix element.
The analysis method of the copper anode furnace slag comprises the following steps of carrying out X-ray fluorescence spectrum analysis on a sample to be detected of the copper anode furnace slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the sample to be detected of the copper anode furnace slag, and specifically comprises the following steps:
and performing X-ray fluorescence spectrum analysis on the sample to be detected of the copper anode furnace slag by using an X-ray fluorescence spectrometer, setting corresponding measurement conditions according to detection elements, and acquiring the fluorescence intensity of each detection element of the sample to be detected of the copper anode furnace slag.
The sample preparation method for the standard sample and/or the sample to be tested of the copper anode furnace slag comprises the following steps:
providing copper anode furnace slag;
crushing, uniformly mixing, dividing, grinding, sieving and drying the copper anode furnace slag to obtain pretreated copper anode furnace slag;
mixing methyl cellulose with the pretreated copper anode furnace slag to obtain mixture powder;
and putting the mixture powder into a tablet press for pressing to obtain the standard sample of the copper anode furnace slag and/or the sample to be tested of the copper anode furnace slag.
The sample preparation method of the standard sample and/or the sample to be tested of the copper anode furnace slag comprises the following steps of:
and (3) crushing, uniformly mixing, dividing, grinding for 5-6min, sieving by using a 180-mesh sieve, and drying in an electrothermal blowing drying oven at 105 +/-5 ℃.
The sample preparation method of the standard sample and/or the sample to be tested of the copper anode furnace slag comprises the step of mixing the methyl cellulose and the pretreated copper anode furnace slag according to the mass ratio of 1: 15-1: 8.
The sample preparation method of the standard sample and/or the sample to be tested of the copper anode furnace slag is characterized in that the purity of the methyl cellulose is greater than or equal to the analytical purity of a chemical reagent.
The sample preparation method of the standard sample of the copper anode furnace slag and/or the sample to be tested of the copper anode furnace slag is characterized in that the working pressure of the tablet press is 30 t-50 t.
Has the advantages that: the invention discloses an analysis method and a sample preparation method of copper anode furnace slag, which have the following advantages compared with the prior art:
1) the analysis speed is high, at least 2 operators are required to continuously operate for 6-8 hours simultaneously for carrying out full analysis on a sample by utilizing a chemical wet method, an inductively coupled plasma emission spectrum and an atomic absorption spectrum, the method only needs 6-8 minutes for completing full element detection of the copper anode slag sample, and the detection efficiency is greatly improved;
2) the element analysis range is wide, the chemical wet method belongs to constant analysis, when the content of the main component of the copper anode slag is too low, the error of the chemical wet method analysis is larger, the analysis method needs to be changed temporarily, and the analysis aging is reduced; the X-ray fluorescence spectrum analysis method can realize trace, trace and constant analysis on each major and minor constituent element of the copper anode slag, and the requirement on the analysis accuracy can be met by one-time analysis;
3) the safety coefficient is high, the environment is friendly, and various dangerous chemicals such as hydrochloric acid, nitric acid, sulfuric acid and the like are needed to be used for chemical wet analysis and inductively coupled plasma emission spectroscopy and atomic absorption spectrophotometry analysis, so that the environment is polluted, and certain influence is caused on the occupational health of operators; the analysis method of the invention only needs to put the sample into the X-ray fluorescence spectrometer, and does not need to carry out additional operation on the sample.
Drawings
Fig. 1 is a flowchart of a method for analyzing copper anode slag according to a preferred embodiment of the present invention.
Fig. 2 is a flowchart of a sample preparation method of a standard sample of copper anode slag and/or a sample to be tested of copper anode slag according to an embodiment of the present invention.
Detailed Description
The invention provides an analysis method and a sample preparation method of copper anode furnace slag, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, the most common analysis method for the contents of main chemical compositions in copper anode furnace slag, such as copper, iron and silicon dioxide, is a chemical wet method, although the classical analysis methods have high accuracy and good precision, because all components can not be measured simultaneously, the wet method is required to be repeated according to the method of each element to dissolve a sample, the operation procedure is complicated, the analysis period is long, and various dangerous chemicals, such as hydrochloric acid, nitric acid, sulfuric acid and the like, are required to be used for dissolving the sample, so that the physical health of an analyst is damaged, and the environment is polluted. Meanwhile, the trace elements such as antimony, bismuth, nickel, lead and the like in the copper anode furnace slag need to be measured by inductively coupled plasma atomic emission spectroscopy or atomic absorption spectroscopy and the like, and the methods still do not get rid of the complicated process of dissolving the sample by a chemical wet method. Therefore, a great deal of labor and time is required to complete the analysis of all the main constituent elements of a copper anode slag sample.
Based on this, the invention provides an analysis method of copper anode furnace slag, referring to fig. 1, which comprises the following steps:
s10, providing a standard sample of the copper anode furnace slag and a sample to be tested of the copper anode furnace slag;
s20, performing X-ray fluorescence spectrum analysis on the copper anode slag standard sample by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the copper anode slag standard sample;
s30, performing matrix effect correction on each detection element of the standard sample of the copper anode slag, and drawing a standard analysis working curve of each detection element of the copper anode slag;
s40, performing X-ray fluorescence spectrum analysis on the copper anode slag to-be-detected sample by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the copper anode slag to-be-detected sample;
s50, obtaining the content of each detection element of the copper anode slag to-be-detected sample according to the fluorescence intensity of each detection element of the copper anode slag to-be-detected sample and the standard analysis working curve of each detection element of the copper anode slag.
Specifically, the method adopts the X-ray fluorescence spectrometry to replace the existing chemical wet analysis, inductively coupled plasma emission spectrometry and atomic absorption spectrophotometry for analyzing the copper anode furnace slag, detects and draws a standard analysis working curve for a standard sample, detects the fluorescence intensity of each detection element of the sample to be detected and compares the fluorescence intensity with the standard analysis working curve to obtain the content of each detection element of the sample to be detected for the copper anode furnace slag, the detection of all elements is only required for 6-8 minutes, the detection efficiency is greatly improved, the trace, trace and constant analysis of each detection element can be realized, the requirement on the analysis accuracy can be met through one-time analysis, meanwhile, no dangerous chemicals are required to be used in the analysis process, the pollution to the environment can be reduced, and the health condition of operators can be guaranteed.
Optionally, the X-ray fluorescence spectrometer is a Zetium PW5400 type X-ray fluorescence spectrometer in Pastinaceae, the Netherlands.
In some embodiments, the detection elements of the copper anode slag include: cu, Fe, Ni, As, Pb, Zn, Sb, Bi, Al 2 O 3 、SiO 2 、MgO、CaO。
In some embodiments, the standard sample of copper anode slag is a production process copper anode slag with a gradient of the content of each detection element from low to high.
In some embodiments, the matrix effect correction is formulated as
Wherein C is i As the concentration of the element to be measured, D i To correct for background values, I i As intensity of the element to be measured, k 0 、k ij To correct the coefficients, I j The strength of the matrix element.
Because the copper anode slag has more detection elements and wider content range of a plurality of elements, the matrix effect is corrected by adopting the self-carried intensity correction function of the instrument, the matrix effect such as the absorption enhancement effect of X-ray fluorescence among the elements is corrected, the influence of the matrix effect on the detection accuracy of each component element in the copper anode slag is eliminated, the correction elements and the related coefficients of each detection element are shown in table 1,
TABLE 1 correction element and correlation coefficient for each detection element
| Element(s) | Correction element | Correlation coefficient |
| Cu | / | 0.99932 |
| Fe | Zn As | 0.99723 |
| Ni | 0.99916 | |
| As | Zn | 0.99948 |
| Pb | Fe | 0.99990 |
| Zn | Cu SiO 2 | 0.99990 |
| Sb | / | 0.99934 |
| Bi | As | 0.99995 |
| Al 2 O 3 | / | 0.99954 |
| SiO 2 | / | 0.99934 |
| MgO | Ca SiO2 | 0.99926 |
| CaO | Pb | 0.99985 |
In some embodiments, the step of performing X-ray fluorescence spectrum analysis on the sample to be detected of copper anode slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the sample to be detected of copper anode slag specifically includes the steps of:
and performing X-ray fluorescence spectrum analysis on the copper anode furnace slag sample to be detected by adopting an X-ray fluorescence spectrometer, setting corresponding measurement conditions according to the detection elements, and acquiring the fluorescence intensity of each detection element of the copper anode furnace slag sample to be detected.
Specifically, the selection of the measurement conditions of each detection element of a standard analysis working curve is crucial to the analysis accuracy of copper anode furnace slag, and generally, the basic principle of the selection of the current and voltage of an X-ray tube is that the current-voltage product is that the higher the working power of a spectrometer is, the higher the detection sensitivity is, for example, the 4KW working power is increased by 33% compared with the 3KW sensitivity and 65% compared with 2.4KW, but the full power can affect the service life of the X-ray tube, so that the full power is generally 0.7-0.9 times of the full power; the voltage set value must be greater than the element excitation potential to be measured, when the applied voltage is 4 times of the element excitation potential to be measured, 90% intensity can be obtained usually, and then the voltage efficiency is improved, the X-ray fluorescence intensity can not be increased much, the light element X-ray fluorescence yield is very low, and the light element X-ray fluorescence intensity can be increased by improving the light element excitation current; selecting K series characteristic spectral lines for Na-Mo and L series characteristic spectral lines for Ta-U according to the spectral line selection rule; the selection principle of the collimator is that 150 mu m has high resolution ratio to the elements between U and K, the 300 mu m has low resolution ratio to the elements between U and K, but the intensity is high, and 700 mu m is suitable for light element analysis between Cl and O; the selection principle of the light splitting crystal is that (1) the resolution is good, which is beneficial to reducing the interference of spectral lines; (2) the diffraction intensity is high; (3) the peak back ratio of the obtained characteristic spectral line after diffraction is large; (4) preferably, no higher order diffraction lines are generated; (5) the temperature and humidity of the crystal are small; the detector selection principle is that detection efficiency and energy resolution ratio are considered; the detection time of a single element is mainly determined according to the counting statistical error requirement and the detection limit requirement, the specific measurement conditions are shown in table 2,
TABLE 2 analysis of measurement conditions for each element detected from copper anode slag by X-ray fluorescence spectrometry
The invention also provides a sample preparation method of the standard sample and/or the sample to be tested of the copper anode furnace slag according to the scheme of the invention, referring to fig. 2, which comprises the following steps:
a10, providing copper anode slag;
a20, crushing, uniformly mixing, dividing, grinding, sieving and drying the copper anode furnace slag to obtain pretreated copper anode furnace slag;
a30, mixing methyl cellulose with the pretreated copper anode furnace slag to obtain mixture powder;
a40, putting the mixture powder into a tablet press for pressing to obtain the standard sample of the copper anode furnace slag and/or the sample to be tested of the copper anode furnace slag.
Specifically, because the content of iron oxide and silicon dioxide in the copper anode furnace slag is high, part of samples cannot be pressed into tablets or the strength of the pressed tablets can be low, and the phenomena of sample cracking, slag falling and the like are easy to occur in the detection process of an X-ray fluorescence spectrometer, so that the X-ray fluorescence spectrometer is damaged and the sample detection cannot be normally completed, the limitation of the X-ray fluorescence spectrum analysis pressing and sample preparation method can be well solved by adding methyl cellulose, and the methyl cellulose belongs to a high-molecular organic polymer, is a powdery particle at normal temperature and is easy to be uniformly mixed with the samples, and meanwhile, the methyl cellulose has good cohesiveness under the high pressure of a sample press and can form a sample tablet with high strength and a smooth surface with the samples; in addition, the methyl cellulose is an organic matter, the X-ray fluorescence yield of carbon and hydrogen is very low, the detection interference on elements in the copper anode slag can be ignored, and the detection elements of the copper anode slag do not contain carbon and hydrogen, so the detection accuracy of the sample cannot be influenced; furthermore, the sample preparation method has the advantages of high safety factor and environmental friendliness, and only needs to protect sample dust in the copper anode slag tabletting process, so that the problems that the environment is polluted and certain influence is caused on the occupational health of operators due to the fact that various dangerous chemicals such as hydrochloric acid, nitric acid and sulfuric acid are needed in chemical wet analysis, inductively coupled plasma emission spectroscopy and atomic absorption spectrophotometry can be avoided.
In some embodiments, the steps of crushing, uniformly mixing, dividing, grinding, sieving, and drying the copper anode slag specifically include:
and (3) crushing, uniformly mixing, dividing, grinding for 5-6min, sieving by using a 180-mesh sieve, and drying in an electrothermal blowing drying oven at 105 +/-5 ℃.
Optionally, the crushing step employs a crusher.
Specifically, the copper anode slag is ground for 5-6min, so that the ground particles of the sample can be guaranteed to be smaller than 90 microns, the sample is fully and uniformly mixed in the grinding process, the passing rate of the sample passing through a 180-mesh (80 microns) sieve can be guaranteed to be more than 99%, the purpose is to enable the X-ray intensity of each element of the copper anode slag sample to tend to be stable, the influence of the granularity effect and the mineral effect of the sample piece can be effectively reduced, and the detection accuracy is effectively improved.
In some embodiments, after obtaining the pretreated copper anode slag, cooling the pretreated copper anode slag to room temperature, and mixing the methylcellulose and the pretreated copper anode slag at a mass ratio of 1:15 to 1:8, wherein the methylcellulose has good cohesiveness under high pressure of a sample press, and can form a sample sheet with high strength and a smooth surface with a sample.
In this embodiment, the step of mixing methyl cellulose with the pretreated copper anode slag to obtain a mixture powder specifically includes:
weighing methyl cellulose and pretreated copper anode furnace slag according to a proportion, mixing, placing in a stainless steel ball milling tank of a vertical square planetary ball mill, placing stainless steel grinding balls, installing the stainless steel ball milling tank, setting revolution at 150rpm, rotation at 200rpm, and running time for 10min to obtain the mixture powder.
In some embodiments, the methylcellulose has a purity greater than or equal to the chemical reagent analytical purity.
Specifically, the purity of the chemical reagent is mainly classified into premium grade purity (GR, 99.8%), analytical purity (AR, 99.7%), and chemical purity (CP, ≧ 99.5%), and in this embodiment, the purity of the methylcellulose is defined as the analytical purity of the chemical reagent and can be prevented from introducing impurities to affect the accuracy of the result of the X-ray fluorescence spectroscopy analysis.
In this embodiment, the step of putting the mixture powder into a tablet press for pressing to obtain the standard sample of the copper anode slag and/or the sample to be tested of the copper anode slag specifically includes:
stirring the mixture powder by using a sample spoon, scooping the mixture powder into the middle part of a PVC sample ring a little by many times, covering a tray without a handle above the sample ring loaded with a sample when the sample is slightly higher than the PVC sample ring, lightly putting the stacked sample pressing trays into the middle of a sample pressing machine pressurizing workbench, pressing a start button to start a sample pressing program, maintaining the pressure for a preset time under the working pressure, automatically releasing the pressure, taking out the sample pressing tray with a sample piece after the sample pressing program is finished, taking down the pressed sample piece, inspecting the surface of the sample piece, and requiring flatness, smoothness and no cracks to obtain the copper anode slag standard sample and/or the copper anode slag sample to be detected, and putting the copper anode slag standard sample and/or the copper anode slag sample to be detected into a sample bag with sample information.
In some embodiments, the working pressure of the tablet press is 30t to 50t and the predetermined time is 10 s.
Specifically, sample sheets meeting the requirements of the X-ray fluorescence spectrometer on the strength and the surface smoothness of the sample can be formed in the working pressure range, and in actual use, the rated working pressure required by pressing the copper anode furnace slag by the copper anode furnace slag pressing machine can be determined by combining with the actual production conditions of enterprises.
Optionally, the tablet press machine adopts Nanjing and Australia ZHY-601A, the size of the PVC sampling ring is phi 30 x 5mm, and the specific equipment selection and size limitation can be adjusted according to actual requirements.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are only a few, and not all, of the present invention, which is intended to be illustrative and not limiting. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The instrumentation and materials used in the following examples were: zetium PW 5400X-ray fluorescence spectrometer of Pasacaceae, Holland, vertical square planetary ball mill, and press into Nanjing and Australia ZHY-601A, PVC sample with a diameter of 30 × 5 mm.
Example 1 sample preparation
The preparation of the standard sample and the sample to be detected adopts the following steps:
1. sample pretreatment: and pouring the dried sample into a crusher for crushing, uniformly mixing, reducing to about 200g by a quartering method, weighing 100g of the sample, grinding for 5-6min, passing the sample through a 180-mesh standard sieve, and drying in an electrothermal blowing drying oven at 105 +/-5 ℃.
2. Mixing methyl cellulose and a sample uniformly: weighing 2g of methylcellulose and 24g of the sample obtained in the step (1) in a stainless steel ball jar of a vertical square planetary ball mill, placing the stainless steel ball in the stainless steel ball jar, installing the stainless steel ball jar, and setting the stainless steel ball jar to revolve at 150rpm, rotate at 200rpm and run for 10min to obtain a uniform mixture of the methylcellulose and the sample.
3. And (3) sample pressing: numbering the samples obtained by the pretreatment in the step 2, stirring the samples by using a sample spoon, scooping the samples into the middle of a PVC sample ring for a small amount of times, covering a tray without a handle above the sample ring loaded with the samples when the samples are slightly higher than the PVC sample ring, lightly putting a stacked sample pressing tray into the middle of a sample pressing machine pressurizing workbench, pressing a start button to start a sample pressing program, automatically relieving pressure after keeping the pressure for 10 seconds at 40t, taking out the sample pressing tray with the sample sheets after the sample pressing program is finished, taking down the pressed sample sheets, checking the surfaces of the sample sheets, and loading the sample sheets into sample bags with sample information to be tested, wherein the sample sheets are flat, smooth and crackless.
Example 2 analysis of copper anode slag
The steps of the analysis of the copper anode slag comprise:
10. providing a standard sample of copper anode furnace slag and a sample to be tested of the copper anode furnace slag;
20. performing X-ray fluorescence spectrum analysis on the standard sample of the copper anode slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the standard sample of the copper anode slag;
30. carrying out matrix effect correction on each detection element of the standard sample of the copper anode slag, and drawing a standard analysis working curve of each detection element of the copper anode slag;
40. performing X-ray fluorescence spectrum analysis on the copper anode slag to-be-detected sample by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the copper anode slag to-be-detected sample;
50. obtaining the fluorescence intensity of each detection element of the copper anode furnace slag to be detected sample and the standard analysis working curve of each detection element of the copper anode furnace slag to obtain Cu, Fe, Ni, As, Pb, Zn, Sb, Bi and Al in the copper anode furnace slag to be detected sample 2 O 3 、SiO 2 MgO and CaO content.
In order to test the reproducibility of the sample preparation method, 10 sample wafers are prepared and measured by the same copper anode slag sample according to the method in example 1, the precision of the sample preparation method is tested, the experimental data are shown in table 3, and the reproducibility of the sample preparation method of the invention adopting the powder tabletting technology is good as can be seen from table 3.
TABLE 3 reproducibility of sample preparation method
In order to test the reproducibility of the analysis method, the same sample is selected for repeated measurement for 10 times, the precision of the analysis method is tested, the experimental data are shown in table 4, and the reproducibility of the analysis method for detecting the copper anode slag sample by the X-ray fluorescence spectrometer is good as shown in table 4.
TABLE 4 reproducibility of analytical methods
In order to verify the accuracy of the analysis method, 8 copper anode slag production process samples with the components in gradient distribution are selected (the content gradient range of part of detection elements is small due to the low content of the part of the detection elements, the coverage of the content gradient range can be met only by correspondingly adjusting along with the content gradient change of high-content detection elements, generally, 8-12 copper anode slag production process samples with the components in gradient distribution can be selected, and the embodiment is preferably 8), the sample preparation method and the analysis method are respectively used for detection and comparison with a chemical wet method, the comparison results of the two methods are shown in tables 5-1 and 5-2, and the results show that the detection results of the copper anode slag and the detection results of the copper anode slag by the chemical wet method accord well, and the requirement of the production on the accuracy of the copper anode slag can be completely met.
Table 5-1 verifies method accuracy test data (. omega/%)
Table 5-2 verifies method accuracy test data (. omega/%)
In summary, the invention discloses an analysis method and a sample preparation method of copper anode furnace slag, which have the following advantages compared with the prior art: 1) the analysis speed is high, at least 2 operators are required to continuously operate for 6-8 hours simultaneously for carrying out full analysis on a sample by utilizing a chemical wet method, an inductively coupled plasma emission spectrum and an atomic absorption spectrum, the method only needs 6-8 minutes for completing full element detection of the copper anode slag sample, and the detection efficiency is greatly improved; 2) the method has good applicability, and the general X-ray fluorescence spectrum analysis tabletting sample preparation method has the problems that the sample can not be pressed or the strength of the pressed sample is low, the surface finish can not meet the detection requirement and the like; 3) the element analysis range is wide, the chemical wet method belongs to constant analysis, when the content of the main component of the copper anode slag is too low, the error of the chemical wet method analysis is larger, the analysis method needs to be changed temporarily, and the analysis aging is reduced; the X-ray fluorescence spectrum analysis method can realize trace, trace and constant analysis on each major and minor constituent element of the copper anode slag, and the requirement on the analysis accuracy can be met by one-time analysis; 4) the safety coefficient is high, the environment is friendly, and various dangerous chemicals such as hydrochloric acid, nitric acid, sulfuric acid and the like are needed to be used for chemical wet analysis and inductively coupled plasma emission spectroscopy and atomic absorption spectrophotometry analysis, so that the environment is polluted, and certain influence is caused on the occupational health of operators; the analysis method of the invention only needs to put the sample into the X-ray fluorescence spectrometer, and does not need to carry out additional operation on the sample.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An analysis method of copper anode slag is characterized by comprising the following steps:
providing a standard sample of copper anode furnace slag and a sample to be tested of the copper anode furnace slag;
performing X-ray fluorescence spectrum analysis on the standard sample of the copper anode slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the standard sample of the copper anode slag;
carrying out matrix effect correction on each detection element of the standard sample of the copper anode slag, and drawing a standard analysis working curve of each detection element of the copper anode slag;
performing X-ray fluorescence spectrum analysis on the copper anode slag to-be-detected sample by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the copper anode slag to-be-detected sample;
and obtaining the content of each detection element of the copper anode furnace slag to-be-detected sample according to the fluorescence intensity of each detection element of the copper anode furnace slag to-be-detected sample and the standard analysis working curve of each detection element of the copper anode furnace slag.
2. The method for analyzing copper anode slag according to claim 1, wherein the detection elements of the copper anode slag include: cu, Fe, Ni, As, Pb, Zn, Sb, Bi, Al 2 O 3 、SiO 2 、MgO、CaO。
3. The method for analyzing copper anode slag according to claim 2, wherein the standard sample of copper anode slag is a production process copper anode slag having a gradient of each detected element content from low to high.
4. The method of analyzing copper anode slag according to claim 1, wherein the formula of the matrix effect correction is
Wherein C i As the concentration of the element to be measured, D i To correct for background values, I i As intensity of the element to be measured, k 0 、k ij To correct the coefficients, I j Is the strength of the matrix element.
5. The method for analyzing the copper anode slag according to claim 1, wherein the step of performing X-ray fluorescence spectrum analysis on the sample to be detected of the copper anode slag by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity of each detection element of the sample to be detected of the copper anode slag specifically comprises the steps of:
and performing X-ray fluorescence spectrum analysis on the copper anode furnace slag sample to be detected by adopting an X-ray fluorescence spectrometer, setting corresponding measurement conditions according to the detection elements, and acquiring the fluorescence intensity of each detection element of the copper anode furnace slag sample to be detected.
6. A sample preparation method for a standard sample and/or a sample to be tested of copper anode slag according to any one of claims 1 to 5, characterized by comprising the steps of:
providing copper anode furnace slag;
crushing, uniformly mixing, dividing, grinding, sieving and drying the copper anode furnace slag to obtain pretreated copper anode furnace slag;
mixing methyl cellulose with the pretreated copper anode slag to obtain mixture powder;
and putting the mixture powder into a tablet press for pressing to obtain the standard sample of the copper anode furnace slag and/or the sample to be tested of the copper anode furnace slag.
7. The sample preparation method of the standard sample and/or the sample to be tested of the copper anode furnace slag according to claim 6, wherein the steps of crushing, uniformly mixing, dividing, grinding, sieving and drying the copper anode furnace slag specifically comprise the steps of:
crushing, uniformly mixing, dividing, grinding for 5-6min, sieving with a 180-mesh sieve, and drying in an electrothermal blowing drying oven at 105 +/-5 ℃.
8. The sample preparation method of the standard sample and/or the sample to be tested of the copper anode slag according to claim 6, characterized in that the methyl cellulose and the pretreated copper anode slag are mixed in a mass ratio of 1: 15-1: 8.
9. The method for preparing the standard sample and/or the sample to be tested of the copper anode furnace slag according to claim 8, wherein the purity of the methyl cellulose is greater than or equal to the analytical purity of a chemical reagent.
10. The sample preparation method for the standard sample and/or the sample to be tested of the copper anode furnace slag according to claim 6, wherein the working pressure of the tablet press is 30 t-50 t.
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