CN115436144A - Sample pretreatment and determination method for detecting heavy metal content in lead concentrate and lead-zinc ore - Google Patents
Sample pretreatment and determination method for detecting heavy metal content in lead concentrate and lead-zinc ore Download PDFInfo
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Abstract
The invention discloses a sample pretreatment and determination method for detecting heavy metal content in lead concentrate and lead-zinc ore, wherein the sample pretreatment method comprises the following steps: 1) Adding aqua regia into a sample to be detected, and putting the sample into an ultrasonic cleaning machine for digestion for 5-10min to digest and carbonize the sample; 2) Transferring the sample treated in the step 1) to a 50mL volumetric flask for constant volume, mixing uniformly, and performing dry filtration to obtain a filtrate for later use; 3) And (3) putting the filtrate into a 50mL volumetric flask, adding aqua regia solution to dilute the filtrate to a scale mark, and uniformly mixing to obtain a sample solution to be detected. The sample pretreatment method is simple in operation process, digestion time is effectively shortened, experiment cost is reduced, heavy metal adsorption and volatilization loss are avoided, pollution to the environment is reduced, detection accuracy and determination efficiency are greatly improved, and rapid determination and accurate measurement of heavy metals are realized.
Description
Technical Field
The invention relates to the technical field of analysis and detection of heavy metal elements, in particular to a sample pretreatment and determination method for detecting the content of heavy metals in lead concentrate and lead-zinc ore.
Background
Lead concentrate and lead-zinc ore are one of the important raw materials for industrial production and are also the main raw materials in the lead smelting industry, in general, lead concentrate and lead-zinc ore of different types contain a certain amount of heavy metal elements, such as copper, arsenic, antimony, bismuth, cadmium and other heavy metals, and the content of the heavy metals in the lead concentrate and the lead-zinc ore directly influences the transaction price and the lead smelting process.
According to the record of the standard of the industry standard YS/T319-2007 lead concentrate: the lead concentrate is divided into four grades according to grades, the lead concentrate of each grade has different requirements on the content of impurity metals, wherein the content of copper in the lead concentrate of the four grades cannot be more than 2.5 percent, and the content of arsenic in the lead concentrate of the four grades cannot be more than 0.7 percent. The chemical components of the lead concentrate are measured according to the regulations of national standards, such as national standards GB/T8152.7-2006, GB/T8152.5-2006, GB/T8152.8-1987 and GB/T8152.12-2006, and in the national standards for measuring the chemical components in the lead concentrate, the pretreatment method for the lead concentrate sample by heavy metal content detection adopts a heating plate digestion method. The specific operation of the electric heating plate digestion method is as follows: (1) Putting the weighed sample into a glass beaker, sequentially adding different inorganic acids, and putting the sample on an electric hot plate at a certain temperature for digestion treatment; (2) Carrying out constant volume on the digested solution by using deionized water to obtain a solution to be detected; (3) And (3) measuring the content of heavy metals such as copper, arsenic, antimony, bismuth, cadmium and the like in the solution to be measured by adopting an Atomic Absorption Spectrometer (AAS), an Atomic Fluorescence Spectrometer (AFS) or a spectrophotometer. However, the electric heating plate digestion method has the problems of large acid consumption, long digestion time, large air pollution, higher experimental cost, easy adsorption and volatilization loss and the like during sample pretreatment
In order to solve the problems, the patent application number CN201910139190.8 discloses an ICP-AES detection method for the content of trace elements in lead concentrate, wherein the trace elements include copper, zinc, cadmium, tin, bismuth, iron, aluminum, manganese, titanium, nickel, chromium, and cobalt elements, and the method aims to solve the problem that the detection of various metal elements in the lead concentrate is inaccurate, especially the content determination of the trace metal elements is inaccurate. The method comprises preparing a sample solution; preparing a working curve standard solution of copper, zinc, cadmium, tin, bismuth, iron, aluminum, manganese, titanium, nickel, chromium and cobalt; measuring the mass concentration of the sample solution and the blank test solution; and calculating the contents of copper, zinc, cadmium, tin, bismuth, iron, aluminum, manganese, titanium, nickel, chromium and cobalt according to a formula. When the method is used for detecting the content of the heavy metal, different inorganic acids are required to be added for stepwise digestion, and the method has the disadvantages of complicated operation steps, long time consumption and large acid consumption. CN201710737798.1 discloses a method for rapidly measuring soil mercury, arsenic, copper, zinc, lead and cadmium by ultrasonic, which comprises a) weighing a high-temperature resistant centrifugal tube, naturally drying in the shade and passing 0.1-0.5 g of soil of 100 meshes; b) 6ml of newly-prepared aqua regia and 2ml of hydrofluoric acid are added; c) Placing the mixture in an ultrasonic digestion tank at normal temperature for 2 hours; d) Cooling, taking out, placing in an oil bath for N minutes, and cooling to a constant volume to be measured; e) The content of each element in the soil was measured by flame atomic absorption measurement, graphite furnace atomic absorption measurement, and atomic fluorescence measurement, respectively. The digestion time for detecting the heavy metal content by adopting the method is 2h, so that the detection method has long time consumption, can not realize rapid determination, and reduces the rate of determining the heavy metal content.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, and provides the sample pretreatment and determination method for detecting the heavy metal content in the lead concentrate and the lead-zinc ore, which is simple to operate, consumes short time and can realize the rapid determination of the heavy metal content.
The technical scheme adopted by the invention for solving the technical problem is as follows: a sample pretreatment method for detecting the content of heavy metals in lead concentrate and lead-zinc ore comprises the following steps: 1) Adding aqua regia into a sample to be detected, and putting the sample into an ultrasonic cleaning machine for digestion for 5-10min to digest and carbonize the sample; 2) Transferring the sample treated in the step 1) to a 50mL volumetric flask for constant volume, uniformly mixing, and performing dry filtration to obtain a filtrate for later use; 3) And (3) putting the filtrate into a 50mL volumetric flask, adding aqua regia solution to dilute to scale marks, and uniformly mixing to obtain a sample solution to be detected.
The sample pretreatment method directly adopts aqua regia as a digestion solution, and digests a sample to be detected by using an ultrasonic cavitation effect at 40-80 ℃ for 5-10min, so that heavy metals of copper, arsenic, antimony, bismuth and cadmium contained in lead concentrate and lead-zinc ore are all extracted into a solution to be the sample solution to be detected, the whole operation process of the pretreatment method is carried out in an open and normal-pressure environment, and can be completed only by using conventional laboratory equipment such as an ultrasonic cleaner, a glass beaker and a volumetric flask, thereby effectively reducing the experiment cost, avoiding the adsorption and volatilization loss of heavy metals and greatly improving the detection accuracy; in the pretreatment method, the digestion time of the sample is 5-10min, so that the digestion time is effectively shortened, unattended operation can be realized during large-scale operation, the determination efficiency is greatly improved, and the rapid determination and accurate measurement of heavy metals are realized.
Further, the dosage of the aqua regia in the step 1) is 5-10mL.
Further, the temperature set in the ultrasonic cleaning machine in the step 1) is 40-80 ℃.
Further, the concentration of the aqua regia in the step 3) is 5%.
Further, the frequency of the ultrasonic cleaning machine is 20-40KHz.
The invention also provides a determination method for detecting the content of heavy metals in lead concentrate and lead-zinc ore, which comprises the following steps: a) Pretreating a sample to be detected by adopting the sample pretreatment method to obtain a sample solution to be detected; b) And (3) determining the content of the heavy metal in the sample solution to be detected by adopting a conventional detection method.
Further, the heavy metal is at least one of copper, arsenic, antimony, bismuth and cadmium.
Further, the conventional detection method in step b) includes inductively coupled plasma emission spectrometer detection, atomic absorption spectrophotometer or atomic fluorescence spectrometer detection.
Further, the detection conditions of the inductively coupled plasma emission spectrometer are as follows: the RF power is 0.8-1.3 kw, the flow rate of cooling gas is 10-15L/min, the flow rate of auxiliary gas is 1.0L/min, and the flow rate of carrier gas is 0.5-1.0L/min; the observation height is 10-15 mm, the washing time is 30-50 s, and the integration time is 30s.
Further, the wavelengths of the inductively coupled plasma emission spectrometer for detecting copper, arsenic, antimony, bismuth and cadmium are 327.396, 193.759, 206.833, 223.061 and 214.438 respectively.
The sample pretreatment and determination method for detecting the heavy metal content in the lead concentrate and the lead-zinc ore has the beneficial effects that:
(1) The sample pretreatment method adopts aqua regia as a digestion solution, and the heavy metals in the sample to be detected are completely extracted into the solution by digestion in an ultrasonic cleaning machine for 5-10min, the sample pretreatment method is simple in operation process, only needs to be operated in a conventional environment, and the used instruments and equipment are simple, so that the experiment cost is effectively reduced, the adsorption and volatilization losses of the heavy metals are avoided, and the detection accuracy is greatly improved; in the pretreatment method, the digestion time of the sample is 5-10min, so that the digestion time is effectively shortened, unattended operation can be realized during large-scale operation, the determination efficiency is greatly improved, and the rapid determination and accurate measurement of heavy metals are realized;
(2) After the sample pretreatment method disclosed by the invention is adopted for treatment, the content of heavy metals in the to-be-detected sample solution can be detected by adopting a conventional method, so that the detection means of lead concentrate and lead-zinc ore are enlarged, the detection means is convenient, and the accuracy of the detection result is improved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Example 1 determination of parameters and Standard Curve of inductively coupled plasma emission Spectroscopy
1. Instruments and reagents
The relevant parameters of the inductively coupled plasma emission spectrometer are as follows: iCAP6300 inductively coupled plasma emission spectrometer (available from Thermo Fisher Scientific, USA); PS-G60 ultrasonic cleaner (from Zijiekang Co.); the concentrations of the copper, arsenic, antimony, bismuth and cadmium are 1000mg/L, and the standard solution is a single element standard solution (national analysis and test center for nonferrous metals and electronic materials); the lead concentrate certified standard substance: GBW07167, wherein the copper content is 0.028 + -0.007%, the arsenic content is 0.173 + -0.014%, the antimony content is 0.089 + -0.012%, the bismuth content is (2), and the cadmium content is 90 + -5 mg/kg; concentrated nitric acid (guaranteed purity); concentrated hydrochloric acid (guaranteed reagent) was purchased from national pharmaceutical group chemical agents, ltd.
2. Standard curve
2.1 preparation of Standard stock solutions of copper, arsenic, antimony, bismuth and cadmium
Taking 10mL of standard solution of copper, arsenic, antimony, bismuth and cadmium with the concentration of 1000mg/L into a 100mL volumetric flask with a single marking line, diluting the standard solution to a scale by using 5% aqua regia solution, and uniformly mixing to obtain the mixed standard stock solution of copper, arsenic, antimony, bismuth and cadmium with the concentration of 100mg/L, wherein the 5% aqua regia is prepared by adopting new-made aqua regia with superior purity and ultrapure water according to the volume ratio of 5: 95.
2.2 preparation of Standard working solution for mixing copper, arsenic, antimony, bismuth and cadmium
Respectively taking 0mL, 0.5mL, 1.0mL, 2.0mL, 5.0mL and 10.0mL of the mixed standard stock solution of copper, arsenic, antimony, bismuth and cadmium of 100mg/L in 2.1, transferring the mixed standard stock solution into a 100mL single-standard volumetric flask, diluting the mixed standard stock solution with water to the concentration, and uniformly mixing to obtain the mixed standard working solution of copper, arsenic, antimony, bismuth and cadmium of which the concentration is 0.0, 0.5, 1.0, 2.0, 5.0 and 10.0mg/L respectively. And detecting the series of standard working solutions by using an inductively coupled plasma emission spectrometer, injecting samples respectively to obtain corresponding spectral intensities, and performing linear regression on the mass concentration (mg/L) by using the spectral intensities. The obtained standard curves are respectively:
y =3789.8913x-27.2270, r =0.999995; as y =63.0315x-0.9274, r =0.999927; y =114.7118x-2.4908, r =0.999812; y =118.2749x-4.6957, r =0.999945; y =1691.7501x-0.4266, r =0.999767; the linear relationship is good.
Example 2
In this embodiment, a lead concentrate marked as GBW07167 as a "blind sample" is selected as a sample to be detected, and the method for detecting the content of heavy metals, such as copper, arsenic, antimony, bismuth and cadmium, in the lead concentrate by using the sample pretreatment method and the determination method of the present invention specifically includes the following steps:
(1) Weighing 0.1g of GBW07167 into a 100mL beaker, adding 10mL of fresh aqua regia, covering the beaker with a watch glass, placing the beaker into an ultrasonic cleaning machine preheated to 40 ℃, and performing ultrasonic digestion for 10min so that all heavy metals contained in the lead concentrate generate corresponding salt solution, and the organic components in the lead concentrate are completely carbonized into black substances;
(2) Taking out the beaker from the ultrasonic cleaning machine, metering the volume of the digested solution into a 50mL volumetric flask, uniformly mixing, and carrying out dry filtration;
(3) Dividing 5mL of filtrate treated in the step (2) into 50mL volumetric flasks, diluting the filtrate with 5% aqua regia solution to scale marks, and uniformly mixing to obtain a sample solution to be detected;
(4) Detecting the contents of copper, arsenic, antimony, bismuth and cadmium in the sample solution to be detected by adopting an inductively coupled plasma emission spectrometer (ICP-AES), wherein the detection conditions of the ICP-AES are shown in Table 1:
TABLE 1 detection conditions for inductively coupled plasma emission spectrometers
The results show that the measured values of copper, arsenic, antimony, bismuth and cadmium in the GBW07167 lead concentrate samples measured by the method of the present invention are 0.029%, 0.177%, 0.093%, 0.013% and 0.009%, respectively. The content of copper in the GBW07167 lead concentrate standard substance is 0.028 +/-0.007%, the content of arsenic is 0.173 +/-0.014%, the content of antimony is 0.089 +/-0.012%, the content of bismuth is (2), and the content of cadmium is 90 +/-5 mg/kg, so that the detection method has high accuracy.
Example 3
In this embodiment, a lead concentrate marked as AF-3111 as a "blind sample" is selected as a sample to be detected, and the method for detecting the content of heavy metals copper, arsenic, antimony, bismuth and cadmium in the lead concentrate by using the sample pretreatment method and the determination method of the present invention specifically includes the following steps:
(1) Weighing 0.1gAF-3111 into a 100mL beaker, adding 10mL of fresh aqua regia, covering the beaker with a watch glass, placing the beaker into an ultrasonic cleaning machine preheated to 40 ℃, and performing ultrasonic decomposition for 10min, so that all heavy metals contained in lead concentrate generate corresponding salt solution, and the organic components in the lead concentrate are completely carbonized into black substances;
(2) Taking out the beaker from the ultrasonic cleaning machine, metering the volume of the digested solution into a 50mL volumetric flask, uniformly mixing, and carrying out dry filtration;
(3) Respectively taking 5mL of filtrate treated in the step (2) into a 50mL volumetric flask, diluting the filtrate to a scale mark by using 5% aqua regia solution, and uniformly mixing to obtain a sample solution to be detected;
(4) Detecting the contents of copper, arsenic, antimony, bismuth and cadmium in the sample solution to be detected by adopting an inductively coupled plasma emission spectrometer (ICP-AES), wherein the detection conditions of the inductively coupled plasma emission spectrometer are shown in Table 1;
the results show that the test values of copper content, arsenic content, antimony content, bismuth content and cadmium content in the AF-3111 lead concentrate sample by the method of the invention are 0.130%, 0.728%, 0.148%, 0.012% and 0.017%, respectively. The recovery rate of copper in AF-3111 lead concentrate is 103.2%, the recovery rate of arsenic is 108.2%, the recovery rate of antimony is 99.8%, the recovery rate of bismuth is 98.4% and the recovery rate of cadmium is 100.1%, so that the detection method has high accuracy.
Example 4
In this embodiment, a lead concentrate marked as AF-2038 as a "blind sample" is selected as a sample to be detected, and the method for detecting the content of heavy metals copper, arsenic, antimony, bismuth and cadmium in the lead concentrate by using the sample pretreatment method and the determination method of the present invention specifically includes the following steps:
(1) Weighing 0.1gAF-3111 into a 100mL beaker, adding 10mL of fresh aqua regia, covering the beaker with a watch glass, placing the beaker into an ultrasonic cleaning machine preheated to 40 ℃, and performing ultrasonic decomposition for 10min, so that all heavy metals contained in lead concentrate generate corresponding salt solution, and the organic components in the lead concentrate are completely carbonized into black substances;
(2) Taking out the beaker from the ultrasonic cleaning machine, metering the volume of the digested solution into a 50mL volumetric flask, uniformly mixing, and carrying out dry filtration;
(3) Respectively taking 5mL of filtrate treated in the step (2) into a 50mL volumetric flask, diluting the filtrate to a scale mark by using 5% aqua regia solution, and uniformly mixing to obtain a sample solution to be detected;
(4) Detecting the contents of copper, arsenic, antimony, bismuth and cadmium in the sample liquid to be detected by adopting an inductively coupled plasma emission spectrometer (ICP-AES), wherein the detection conditions of the ICP-AES are shown in Table 1;
the results show that the measured value of the content of copper, the measured value of the content of arsenic, the measured value of antimony, the measured value of bismuth and the measured value of cadmium in the AF-2038 lead concentrate sample detected by the method of the invention are respectively 3.73%, 0.260%, 0.109% and 0.230%, respectively. The results of the atomic absorption method and the atomic fluorescence method for AF-2038 lead concentrates are known as follows: the content of copper is 3.70%, the content of arsenic is 0.220%, the content of antimony is 0.105%, the content of bismuth is 0.222%, and the content of cadmium is 0.059%, so that the detection method has high accuracy.
Example 5
In this embodiment, the ultrasonic digestion time is set to be 5min for testing, so as to determine whether the ultrasonic digestion time of 5min can achieve an ideal digestion effect.
Selecting lead concentrate marked as GBW (E) 070080 as a 'blind sample' for detection, and specifically comprising the following steps:
(1) Weighing 0.1g of GBW (E) 070080 in a 100mL beaker, adding 10mL of fresh aqua regia, covering the beaker with a surface dish, placing the beaker in an ultrasonic cleaning machine preheated to 40 ℃, and performing ultrasonic digestion for 5min so that all heavy metals contained in lead concentrate generate corresponding salt solution, and the organic components in the lead concentrate are completely carbonized into black substances;
(2) Taking out the beaker from the ultrasonic cleaning machine, metering the volume of the digested solution into a 50mL volumetric flask, uniformly mixing, and carrying out dry filtration;
(3) Dividing 5mL of the filtrate treated in the step (2) into 50mL volumetric flasks, diluting the filtrate with 5% aqua regia solution to scale marks, mixing the filtrate and the water solution uniformly to obtain a sample solution to be detected,
(4) Detecting the contents of copper, arsenic, antimony, bismuth and cadmium in the sample liquid to be detected by adopting an inductively coupled plasma emission spectrometer (ICP-AES), wherein the detection conditions of the ICP-AES are shown in Table 1:
the results show that the measured values of copper content, arsenic content, antimony content and cadmium content in the GBW (E) 070080 lead-zinc ore sample detected by the method of the invention are 0.069%, 0.137%, 0.042% and 0.064%, respectively. The GBW (E) 070080 lead-zinc ore standard substance is known to have the copper content of 0.071 +/-0.002%, the arsenic content of 0.138 +/-0.002%, the antimony content of 0.044 +/-0.002% and the cadmium content of 0.066 +/-0.002%, so that the invention has higher accuracy even when the ultrasonic digestion time is 5 min.
Example 6 detection Limit test, linear Range and comparison test of the detection methods of the invention
1. Limit of detection test
After 11 beakers were taken and no sample was added, the pretreatment and the test were carried out by exactly the same procedure as in example 2, i.e., a blank test was carried out, and the measurement results are shown in table 2.
TABLE 2 detection results of blank test
The sample detection limit SDL is less than or equal to 500 x 3s, and the dilution ratio is 500 according to the sample weighing 0.1g and the dilution volume 50mL, namely 500 is a coefficient required by converting the solution concentration into the content of the substance to be detected in the sample.
2. Linear Range of the detection method of the invention
2.1 in daily detection, the standard series solutions of 0, 0.5, 1.0, 2.0, 5.0 and 10.0mg/L are used for drawing a curve all the time, and the linearity is good.
2.2 for the linear range of the detection method of the invention, prepare the standard series with concentration of 0, 0.5, 1, 2, 5, 10.0mg/L respectively, adopt the inductively coupled plasma emission spectrometer to detect the said series of standard working solutions, inject the sample separately, obtain the corresponding spectral intensity, make the linear regression to the mass concentration (mg/L) with the spectral intensity, the standard curve to get copper, arsenic, antimony, bismuth, cadmium is:
Cu:y＝4740.9935x–9.0618，r＝0.999905；As:y＝77.3364x–2.3705，r＝0.999067；Sb:y＝114.7118x–2.4908，r＝0.999812；Bi:y＝118.0924x-2.6688，r＝0.999766；Cd:y＝2536.3290x-0.5380，r＝0.999689；
as can be seen, the detection method of the invention has good linear relation in the range of 0-10 mg/L.
3. Comparison test
In order to illustrate the accuracy of the detection method, taking the detection of the contents of copper, arsenic, antimony, bismuth and cadmium in lead concentrate as an example, comparison tests are performed under different operating environments, wherein arsenic is the most difficult one of all heavy metals.
3.1 human alignment
(1) In a laboratory, different operators perform detection on the contents of copper, arsenic, antimony, bismuth and cadmium in the lead concentrate with the AF-3111 number for 7 times respectively under the recurrent condition by adopting the detection method, and the detection results are shown in Table 3.
TABLE 3 comparison of the contents of Cu, as, sb, bi and Cd in different operators
(2) Variance test (F test)
For Cu, the average value of the A determination is
Standard deviation S First of all ＝0.0032；
B measures an average value of
Standard deviation S Second step ＝0.0019；
Looking up the table to obtain F 0.95(6,7) =4.21, F < F is seen 0.95(6,7) It is shown that there is no significant difference in the copper variance between the two sets of data.
For As, the average values of A determined are
Standard deviation S First of all ＝0.0144；
B measured on an average of
Standard deviation S Second step ＝0.0152；
Looking up the table to obtain F 0.95(6,7) =4.21, F < F is seen 0.95(6,7) It is shown that there is no significant difference in the copper variance between the two sets of data.
For Sb, the average value of the A measurement was
Standard deviation S First of all ＝0.0013；
B measured on an average of
Standard deviation S Second step ＝0.0024；
Looking up the table to obtain F 0.95(6,7) =4.21, F < F is seen 0.95(6,7) It shows that the copper variance of the two groups of data is not significant and poorAnd (3) performing exception.
For Bi, the average value of the A determination is
Standard deviation S First of all ＝0.0021；
B measured on an average of
Standard deviation S Second step ＝0.0017；
F is obtained by looking up the table 0.95(6,7) =4.21, F < F is seen 0.95(6,7) It is shown that there is no significant difference in the copper variance between the two sets of data.
For Cd, the average A value was determined to be
Standard deviation S First of all ＝0.0011；
B measured on an average of
Standard deviation S Second step ＝0.0008；
Looking up the table to obtain F 0.95(6,7) =4.21, F < F is seen 0.95(6,7) It is shown that there is no significant difference in the copper variance between the two sets of data.
(3) Mean value test (t test)
For Cu, t a/b =2.13. Taking alpha =0.05, and checking a double-side inspection t value table to obtain t (0.05, 12) =2.18; there was no significant difference in the mean values of the two sets of data, t A/B < t (0.05, 12).
For As, t a/b =0.88. Taking alpha =0.05, and checking a double-side inspection t value table to obtain t (0.05, 12) =2.18; there was no significant difference in the mean values of the two sets of data, t A/B < t (0.05, 12).
For Sb, t a/b =1.94. Taking alpha =0.05, and checking a double-side inspection t value table to obtain t (0.05, 12) =2.18; the mean values of the two groups of data with t A/B < t (0.05, 12) have no significant difference.
For Bi, t a/b =1.96. Taking alpha =0.05, and checking a double-side inspection t value table to obtain t (0.05, 12) =2.18; the mean values of the two groups of data with t A/B < t (0.05, 12) have no significant difference. .
For Cd, t a/b =1.94. Taking alpha =0.05, and looking up a double-side inspection t value table to obtain t (0.05, 12) =2.18. The mean values of the two data groups were not significantly different.
In conclusion, when the method is used for pretreatment and detection, the data of different operators have no significant difference, and the method has good consistency and comparability.
3.2 method alignment
The lead concentrate samples GBW07167, AF-3108, AF-3111 and AF-3113 are used as samples to be detected, the method is adopted to carry out comparison detection on copper, arsenic, antimony, bismuth and cadmium by an atomic absorption method (AAS), an Atomic Fluorescence Spectrometry (AFS) and a sodium hypophosphite titration method, each sample is subjected to parallel detection for 5 times, and the detection results are shown in Table 4, so that the measured value and the nominal value of the method are not obviously different.
TABLE 4 comparative test results/W% of Cu, as, sb, bi and Cd contents in Pb concentrate
Example 7 precision and accuracy of the assay of the invention
The method for detecting the content of copper, arsenic, antimony, bismuth and cadmium in the lead concentrate has the advantages that the lead concentrate AF-3111 is used as a detection sample, the sample is pretreated and detected according to the method, the detection is repeated 11 times, and the measured values of the content of copper, arsenic, antimony, bismuth and cadmium, the average value, the relative standard deviation and the recovery rate of the measured values are 10 times of parallel detection AF-3111 as shown in Table 5.
TABLE 5 test results of precision and accuracy of the methods
It should be noted that the detection instruments used in the detection methods of embodiments 2 to 5 of the present invention are all inductively coupled plasma emission spectrometers, and as an alternative implementation, those skilled in the art may also select an atomic absorption spectrophotometer as an instrument for detecting copper, antimony, bismuth, and cadmium, and an atomic fluorescence spectrometer as an instrument for detecting arsenic.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A sample pretreatment method for detecting the content of heavy metals in lead concentrate and lead-zinc ore is characterized by comprising the following steps: the method comprises the following steps: 1) Adding aqua regia into a sample to be detected, and putting the sample into an ultrasonic cleaning machine for digestion for 5-10min to digest and carbonize the sample; 2) Transferring the sample treated in the step 1) to a 50mL volumetric flask for constant volume, uniformly mixing, and performing dry filtration to obtain a filtrate for later use; 3) And (3) putting the filtrate into a 50mL volumetric flask, adding aqua regia solution to dilute the filtrate to a scale mark, and uniformly mixing to obtain a sample solution to be detected.
2. The sample pretreatment method for detecting the content of heavy metals in lead concentrate and lead-zinc ore according to claim 1, characterized in that: the dosage of the aqua regia in the step 1) is 5-10mL.
3. The sample pretreatment method for detecting the content of heavy metals in lead concentrate and lead-zinc ore according to claim 1, characterized in that: the temperature set in the ultrasonic cleaning machine in the step 1) is 40-80 ℃.
4. The sample pretreatment method for detecting the content of heavy metals in lead concentrate and lead-zinc ore of claim, which is characterized by comprising the following steps: the concentration of the aqua regia in the step 3) is 5 percent.
5. The sample pretreatment method for detecting the content of heavy metals in lead concentrate and lead-zinc ore of claim, which is characterized by comprising the following steps: the frequency of the ultrasonic cleaning machine is 20-40KHz.
6. A method for detecting the content of heavy metals in lead concentrate and lead-zinc ore is characterized by comprising the following steps: the method comprises the following steps: a) Pretreating a sample to be detected by adopting the sample pretreatment method as claimed in any one of claims 1 to 5 to obtain a sample solution to be detected; b) And (3) determining the content of the heavy metal in the sample solution to be detected by adopting a conventional detection method.
7. The method for detecting the content of the heavy metals in the lead concentrate and the lead-zinc ore according to claim 6, wherein the method comprises the following steps: the heavy metal is at least one of copper, arsenic, antimony, bismuth and cadmium.
8. The method for detecting the content of the heavy metals in the lead concentrate and the lead-zinc ore according to claim 7, characterized by comprising the following steps: the conventional detection method in the step b) comprises detection of an inductively coupled plasma emission spectrometer, detection of an atomic absorption spectrophotometer or detection of an atomic fluorescence spectrometer.
9. The method for detecting the content of the heavy metals in the lead concentrate and the lead-zinc ore according to claim 8, wherein the method comprises the following steps: the detection conditions of the inductively coupled plasma emission spectrometer are as follows: the RF power is 0.8-1.3 kw, the flow rate of cooling gas is 10-15L/min, the flow rate of auxiliary gas is 1.0L/min, and the flow rate of carrier gas is 0.5-1.0L/min; the observation height is 10-15 mm, the washing time is 30-50 s, and the integration time is 30s.
10. The method for detecting the content of the heavy metals in the lead concentrate and the lead-zinc ore according to claim 8, characterized by comprising the following steps: the wavelengths of the inductively coupled plasma emission spectrometer for detecting copper, arsenic, antimony, bismuth and cadmium are 327.396, 193.759, 206.833, 223.061 and 214.438 respectively.
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