阅读说明：本技术 测定锌液中铝元素、铁元素、镉元素和铅元素含量的方法 (Method for measuring contents of aluminum element, iron element, cadmium element and lead element in zinc liquid ) 是由 嵇龙 喻能利 蔡璐 戴国宣 周露 方利红 吴振 于 2019-10-11 设计创作，主要内容包括：本发明公开了一种测定锌液中铝元素、铁元素、镉元素和铅元素含量的方法,包括步骤：S1、取样；S2、制样：对锌锭试样进行铣削,控制刀具的进刀径程在50-250mm/min范围内,控制刀具的转速在300-800r/min范围内；S3、试样测定：采用X射线荧光光谱仪对锌锭试样进行检测。本发明的测定锌液中铝元素、铁元素、镉元素和铅元素含量的方法,通过对铣削参数的控制,提高锌锭试样分析面的光洁度,从而可以满足采用X射线荧光法的测定要求。(The invention discloses a method for measuring the contents of aluminum element, iron element, cadmium element and lead element in zinc liquid, which comprises the following steps: s1, sampling; s2, sample preparation: milling a zinc ingot sample, controlling the feed diameter range of a cutter within 50-250mm/min, and controlling the rotating speed of the cutter within the range of 300-800 r/min; s3, sample measurement: and detecting the zinc ingot sample by adopting an X-ray fluorescence spectrometer. The method for measuring the contents of the aluminum element, the iron element, the cadmium element and the lead element in the zinc liquid improves the smoothness of the analysis surface of a zinc ingot sample by controlling milling parameters, thereby meeting the measurement requirement of an X-ray fluorescence method.)

1. The method for determining the contents of aluminum element, iron element, cadmium element and lead element in the zinc liquid is characterized by comprising the following steps:

s1, sampling;

s2, sample preparation: milling a zinc ingot sample, controlling the feed diameter range of a cutter within 50-250mm/min, and controlling the rotating speed of the cutter within the range of 300-800 r/min;

s3, sample measurement: and detecting the zinc ingot sample by adopting an X-ray fluorescence spectrometer.

2. The method for determining the contents of aluminum, iron, cadmium and lead in zinc solution according to claim 1, wherein in step S2, the cutting diameter of the tool is controlled to 50mm/min, and the rotation speed of the tool is controlled to 800 r/min.

3. The method for determining the contents of aluminum, iron, cadmium and lead in zinc solution according to claim 1 or 2, wherein in step S2, the milling depth of the zinc ingot sample is controlled to be 0.9-1.2mm, and a plurality of times of milling are performed, and the feed amount of each time of milling is controlled to be the same or different.

4. The method according to claim 3, wherein in step S2, the zinc ingot sample is milled three times, and the amount of feed is controlled to be 0.2-0.5mm when the zinc ingot sample is milled for the first time; when the zinc ingot sample is milled for the second time, controlling the feed amount to be 0.2-0.5 mm; when the zinc ingot sample is milled for the third time, the feed amount is controlled to be 0.1-0.2 mm.

5. The method for determining the contents of aluminum, iron, cadmium and lead in zinc liquid according to claim 3 or 4, wherein in said step S2, the milling depth of the zinc ingot sample is controlled to 1.0 mm.

6. The method for determining the contents of Al, Fe, Cd and Pb in Zn according to any one of claims 1 to 5, wherein in step S3, a working curve for X-ray fluorescence analysis of the contents of Al, Fe, Cd and Pb in Zn is plotted to determine the parameters of analysis line, X-ray tube voltage, X-ray tube current, analysis crystal, detector and measurement time.

Technical Field

The invention belongs to the technical field of element content determination, and particularly relates to a method for determining the content of aluminum elements, iron elements, cadmium elements and lead elements in a zinc solution.

Background

At present, inductively coupled plasma emission spectrometry (ICP) is adopted for analyzing the content of aluminum, iron, cadmium and lead in zinc liquid, and the method needs sample drilling, sample weighing, sample dissolving and ICP detection. Each batch of samples takes 40-60 minutes from receiving to reporting, and when the data is abnormal and needs to be rechecked, the analysis data is difficult to report in a short time.

When the X-ray fluorescence method is adopted to measure the zinc liquid sample, certain requirements are provided for the shape and the size of the zinc liquid sample, the components of the zinc liquid sample are required to be uniform, and the analysis surface of the sample is required to be flat, smooth and crackless. The smoothness of the sample analysis surface directly affects the measured X-ray intensity, to which the light element aluminum in the zinc bath is particularly sensitive. The prior art lacks a means for improving the smoothness of the analysis surface of the zinc liquid sample.

Due to the problems, the method for measuring the contents of aluminum element, iron element, cadmium element and lead element in the zinc liquid by using an X-ray fluorescence method is difficult to realize.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for measuring the contents of aluminum, iron, cadmium and lead in zinc liquid, aiming at improving the smoothness of the analysis surface of a zinc ingot sample and meeting the measurement requirement of an X-ray fluorescence method.

In order to achieve the purpose, the invention adopts the technical scheme that: the method for measuring the contents of aluminum element, iron element, cadmium element and lead element in the zinc liquid comprises the following steps:

s1, sampling;

s2, sample preparation: milling a zinc ingot sample, controlling the feed diameter range of a cutter within 50-250mm/min, and controlling the rotating speed of the cutter within the range of 300-800 r/min;

s3, sample measurement: and detecting the zinc ingot sample by adopting an X-ray fluorescence spectrometer.

In the step S2, the cutting diameter of the cutter is controlled to be 50mm/min, and the rotation speed of the cutter is controlled to be 800 r/min.

In the step S2, the milling depth of the zinc ingot sample is controlled to be 0.9-1.2mm, and multiple times of milling are performed, and the feed amount of each time of milling is controlled to be the same or different.

In the step S2, the zinc ingot sample is milled three times, and the feed amount is controlled to be 0.2-0.5mm when the zinc ingot sample is milled for the first time; when the zinc ingot sample is milled for the second time, controlling the feed amount to be 0.2-0.5 mm; when the zinc ingot sample is milled for the third time, the feed amount is controlled to be 0.1-0.2 mm.

In step S2, the milling depth of the zinc ingot sample was controlled to 1.0 mm.

In the step S3, a working curve for analyzing the contents of aluminum, iron, cadmium, and lead in the zinc solution by using an X-ray fluorescence method is drawn, and an analysis line, an X-ray tube voltage, an X-ray tube current, an analysis crystal, a detector, and a measurement time parameter are determined.

The method for determining the contents of the aluminum element, the iron element, the cadmium element and the lead element in the zinc liquid has the following advantages:

(1) by controlling milling parameters, the smoothness of the analysis surface of the zinc ingot sample is improved, so that the measurement requirement of an X-ray fluorescence method can be met;

(2) the contents of aluminum element, iron element, cadmium element and lead element in the zinc liquid are determined by adopting an X-ray fluorescence method, the inspection period is shortened to about 10min, and the production inspection requirements are met;

(3) the use of acid and alkali chemical reagents is reduced, the discharge of waste liquid is reduced, and the requirements of modern enterprises on energy conservation, emission reduction and low-carbon production are met;

(4) the labor intensity is reduced, the human resource cost is reduced, the problem of insufficient personnel is relieved, and the optimization of an inspection team is facilitated;

(5) the method can solve the problems that the shape, the size and the uniformity of a zinc liquid sample meet the requirement of X-ray fluorescence measurement and the problem exists in the preparation of the zinc liquid sample, thereby establishing a working curve of an X-ray fluorescence spectrometry and realizing the rapid and accurate measurement of the contents of aluminum, iron, cadmium and lead in the zinc liquid by adopting the X-ray fluorescence spectrometry.

Drawings

The description includes the following figures, the contents shown are respectively:

FIG. 1 is a flow chart of the method for determining the contents of aluminum, iron, cadmium and lead in zinc liquid according to the present invention;

FIG. 2 is a schematic structural view of a zinc ingot sample;

FIG. 3 is a graph showing the influence of the waiting time after sample preparation on the aluminum content of the sample surface.

Detailed Description

The following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings for a purpose of helping those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solution of the present invention and to facilitate its implementation.

As shown in figure 1, the invention provides a method for measuring the contents of aluminum, iron, cadmium and lead in zinc liquid, which comprises the following steps:

s1, sampling;

s2, sample preparation: milling a zinc ingot sample, controlling the feed diameter range of a cutter within 50-250mm/min, and controlling the rotating speed of the cutter within the range of 300-800 r/min;

s3, sample measurement: and detecting the zinc ingot sample by adopting an X-ray fluorescence spectrometer.

Specifically, in step S1, a zinc ingot sample is taken using a sampling die made of brass as a lining material. When the sampling mold is used for sampling, the zinc ingot sample can be well stripped from the brass mold, the service life of the sampling mold is prolonged, and the shape and the size of the zinc ingot sample are determined.

As shown in FIG. 2, the zinc ingot sample has a cylindrical structure, the diameter of the zinc ingot sample is 30-50mm, and the length of the zinc ingot sample is 15-30 mm.

Preferably, in step S2, the zinc ingot sample is milled by using a sample milling machine, the cutting diameter of the cutter of the sample milling machine is controlled to be 50mm/min, and the rotation speed of the cutter of the sample milling machine is controlled to be 800 r/min. Under the cutter feeding path and the rotating speed, the relative standard deviation of aluminum element, iron element, cadmium element and lead element measured after milling is minimum, and the smoothness of the surface (namely an analysis surface) of the zinc ingot sample can be improved.

In order to confirm the influence of milling with different diameter ranges and rotating speed parameters on the fluorescence intensity of aluminum elements, iron elements, cadmium elements and lead elements in zinc liquid, the same zinc ingot sample is milled by using a feed diameter range of 50mm/min, a cutter rotating speed of 800r/min, a feed diameter range of 150mm/min, a cutter rotating speed of 550r/min, a feed diameter range of 250mm/min and a cutter rotating speed of 300r/min, and the zinc ingot sample is detected once by using an X-ray fluorescence spectrometer after being milled once, and the measurement results are shown in a table 1 and a table 2. As can be seen from tables 1 and 2, when the zinc ingot sample is milled with the cutting diameter of the cutter of the sample milling machine set to 50mm/min and the cutter rotating speed set to 800r/min, the measured relative standard deviation of the aluminum element, the iron element, the cadmium element and the lead element of the zinc ingot sample is the smallest, and the surface smoothness of the zinc ingot sample is the best. Therefore, the diameter stroke is 50mm/min, and the rotating speed is 800r/min, which is the best milling parameter.

Table 1: milling experimental data by using different diameter ranges (mm/min) and rotating speeds (r/min)

Table 2: experimental data continuation table milled by different diameter ranges (mm/min) and rotating speeds (r/min)

In the step S2, the milling depth of the zinc ingot sample is controlled to be 0.9-1.2mm, and the milling is performed for a plurality of times, and the feed amount of each milling is controlled to be the same or different. The cutter of the milling machine is model SEMT1204AGN HK 3205.

In this embodiment, in step S2, the zinc ingot sample is milled three times, and the feed amount is controlled to be 0.2 to 0.5mm when the zinc ingot sample is milled for the first time; when the zinc ingot sample is milled for the second time, controlling the feed amount to be 0.2-0.5 mm; when the zinc ingot sample is milled for the third time, the feed amount is controlled to be 0.1-0.2 mm. In step S2, the milling depth of the zinc ingot sample was controlled to 1.0 mm. By controlling the milling depth and milling for multiple times, the problems of concave surface, inclusion, surface oxidation and the like of the zinc ingot sample analysis surface can be effectively solved, and the smoothness of the zinc ingot sample analysis surface can be further improved.

In order to confirm the element distribution of the bulk zinc ingot samples at different milling depths, the same zinc ingot sample was milled 1 time by the milling machine and measured 1 time and 10 times in total, and the measurement results are shown in table 3, and it can be seen from table 3 that the aluminum element, iron element, cadmium element and lead element of the zinc ingot sample were uniformly distributed at different depths.

Table 3: results of different depth measurements on bulk samples

In the step S3, a working curve for analyzing the contents of al, fe, cd and pb in the molten zinc by X-ray fluorescence is drawn, and an analysis line, an X-ray tube voltage, an X-ray tube current, an analysis crystal, a detector and a measurement time parameter are determined.

The working conditions of the X-ray fluorescence spectrometer, the linear regression equation of each element and the correlation coefficient are shown in tables 4 and 5. And when a working curve is drawn, the standard sample is measured according to the working conditions of the X-ray fluorescence spectrometer, and linear regression is carried out by taking the content of each element as an abscissa and the fluorescence intensity as an ordinate.

Table 4: elemental measurement conditions

Table 5: linear regression equation, correlation coefficient

Element(s)	Linear regression equation	Correlation coefficient
			AL	y＝0.27x-0.0133	0.9993
Fe	y＝0.006x-0.0276	0.9991
			Pb	y＝0.0232x-0.2201	0.9998
Cd	y＝0.0383x-0.2194	0.9992

In step S3, after the zinc ingot sample is prepared, the prepared zinc ingot sample should be immediately detected by an X-ray fluorescence spectrometer in order to prevent the aluminum element on the surface of the sample from being oxidized. The effect of the waiting time after sample preparation on the aluminum content of the sample surface is shown in table 6 and fig. 3.

Table 6: influence of waiting time after sample preparation on AL content on sample surface

And (3) determining the element determination range, selecting zinc liquid standard samples with high, medium and low content ranges for determination, and comparing the zinc liquid standard samples with the standard values. The comparison result is good, the quality control requirement in the production process is met, and the measurement result is shown in table 7. The experimental data in Table 7 can determine the measuring ranges of aluminum, iron, lead and cadmium in the method, which are shown in Table 8.

Table 7: measured data of standard sample

Table 8: elements and measurement ranges

In order to calculate the standard deviation of aluminum, iron, lead and cadmium in different content ranges, the method is adopted to mill the S-5 and D-4 zinc liquid samples on a milling machine for 1 time and measure 1 time and 10 times in total, and the measurement results are listed in tables 9 and 10.

The allowable difference of the method can be calculated from tables 9 and 10, which are shown in Table 11.

The unknown sample is milled by a milling machine and then is measured on the X-ray fluorescence spectrometer, the comparison of the measurement result and the chemical value is shown in the table 12, and the result in the table 12 shows that the measurement value of the X-ray fluorescence spectrometer has good effect from the comparison result of the method and meets the quality control requirement of the production process.

Table 9: sample block S-5 analysis standard deviation table

Number of analyses	AL，％	Cd，％	Fe，％	Pb，％
					1	0.276	0.0045	0.0105	0.0035
2	0.275	0.0041	0.0108	0.0034
					3	0.266	0.0046	0.0107	0.0033
4	0.275	0.0043	0.0109	0.0032
					5	0.273	0.0042	0.0106	0.0035
6	0.276	0.0043	0.0107	0.0034
					7	0.280	0.0042	0.0108	0.0035
8	0.278	0.0044	0.0106	0.0032
					9	0.270	0.0046	0.0108	0.0035
10	0.270	0.0045	0.0106	0.0034
					Mean value of	0.2739	0.00437	0.0107	0.00339
Standard deviation of	0.004202	0.000177	0.000125	0.000120

Table 10: sample block D-4 analysis standard deviation table

Table 11: method allowance table

Table 12: comparison of the X-ray fluorescence measurement results with the chemical analysis values

The invention is described above with reference to the accompanying drawings. It is to be understood that the specific implementations of the invention are not limited in this respect. Various insubstantial improvements are made by adopting the method conception and the technical scheme of the invention; the present invention is not limited to the above embodiments, and can be modified in various ways.