CN113252647B - Method for measuring contents of copper, tin and bismuth in lead smelting solid waste with high silver content - Google Patents
Method for measuring contents of copper, tin and bismuth in lead smelting solid waste with high silver content Download PDFInfo
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Abstract
The application provides a method for measuring the contents of copper, tin and bismuth in lead smelting solid waste with high silver content. The method for measuring the contents of copper, tin and bismuth in the lead smelting solid waste with high silver content comprises the following steps: carrying out alkali fusion treatment on the lead smelting solid waste to obtain an alkali melt, and leaching the alkali melt by using a mixed solution to obtain a solution to be detected; measuring the solution to be measured by using an ICP-AES method, and calculating the contents of copper, tin and bismuth in the lead smelting solid waste through a standard solution working curve; the mixed solution comprises a mixture of tartaric acid and reverse aqua regia, and the mass content of silver in the lead smelting solid waste is 0.5-20%. The determination method provided by the application can realize simultaneous detection of the contents of copper, tin and bismuth, and has the advantages of short time consumption, high efficiency, high detection precision, wide range and high standard addition recovery rate.
Description
Technical Field
The application relates to the field of metal detection, in particular to a method for determining the content of copper, tin and bismuth in lead smelting solid waste with high silver content.
Background
The hazardous wastes generated in the lead smelting process mainly comprise alkaline residue, anode mud and soot, and the method for researching, analyzing and determining copper, tin and bismuth in the samples has very practical significance.
At present, the commonly used analysis methods of the samples comprise a wet analysis method, a photometric method, a volumetric method and an X-ray fluorescence spectrometry method, and the methods usually have long analysis period and complex operation and can not meet the requirement of the current rapid analysis.
Because the complexity of the samples brings difficulty to the pretreatment of the samples, the prior art adopts a method of treating the samples by hydrochloric acid-tartaric acid-hydrogen peroxide, and the hydrogen peroxide has oxidability in an acid environment, so that tin can be always kept in a high valence state, the tin can be better complexed with tartaric acid, and the phenomenon that the result is lower due to metastannic acid generated by unstable tin is avoided. However, in the actual treatment of lead smelting solid waste containing some gold and silver materials, the hydrolysis phenomenon of part of samples cannot be completely eliminated by treating the samples with hydrochloric acid-tartaric acid-hydrogen peroxide. The main reason is that the lead smelting solid waste sample has complex composition, the material usually contains Au, Ag, Se, Te, As, Sb, Bi and Sn, and exists in various phases, and the solution is easy to be turbid due to the formation of hydroxide of transition metal which is difficult to oxidize after pretreatment.
The development of a method which is simple in sample treatment and can rapidly and accurately measure the contents of copper, tin and bismuth in the lead smelting solid waste simultaneously becomes a technical problem to be solved urgently.
Disclosure of Invention
The application aims to provide a method for measuring the contents of copper, tin and bismuth in lead smelting solid waste with high silver content, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a method for measuring the contents of copper, tin and bismuth in lead smelting solid waste with high silver content comprises the following steps:
carrying out alkali fusion treatment on the lead smelting solid waste to obtain an alkali melt, and leaching the alkali melt by using a mixed solution to obtain a solution to be detected;
measuring the solution to be measured by using an ICP-AES method, and calculating the contents of copper, tin and bismuth in the lead smelting solid waste through a standard solution working curve;
the mixed solution comprises a mixture of tartaric acid and reverse aqua regia, and the mass content of silver in the lead smelting solid waste is 0.5-20%.
Preferably, the alkali melt processing comprises: and mixing the lead smelting solid waste with sodium peroxide, and heating and melting.
Preferably, the mass ratio of the lead smelting solid waste to the sodium peroxide is (0.05-0.15): 1.
preferably, the heating temperature is 600-800 ℃, and the time for keeping the molten state is 20-40 min.
Preferably, the mass-to-volume ratio of the tartaric acid to the reverse aqua regia is (0.2-2) g: (25-30) ml.
Preferably, the mass-to-volume ratio of the tartaric acid to the reverse aqua regia is 1 g: (25-30) ml.
Preferably, the standard solution working curve is obtained by:
and measuring a plurality of copper, tin and bismuth mixed standard solutions with different concentrations by using an ICP-AES method, and fitting by taking the concentration value as an abscissa and the signal intensity value as an ordinate to obtain a working curve of the standard solution.
Preferably, a sample blank solution is added into the mixed standard solution;
the preparation method of the sample blank solution comprises the following steps: and carrying out alkali fusion treatment without adding the lead smelting solid waste, and then leaching by using the mixed solution to obtain the sample blank solution.
Preferably, in the measuring process, the operating conditions of the inductively coupled plasma emission spectrometer are specifically as follows:
the RF power is 1000W-1200W, the plasma air flow is 12.0-18.0L/min, the auxiliary air flow is 0-2.25L/min, the atomizing air flow is 0.60L/min-0.70L/min, and the observation height is 4mm-8 mm.
Preferably, during the determination, the wavelengths of the analysis elements are respectively: 327.395nm of copper, 189.925nm of tin and 223.061nm of bismuth.
Compared with the prior art, the beneficial effect of this application includes:
according to the method for determining the contents of copper, tin and bismuth in the lead smelting solid waste with high silver content, the mixed solution containing tartaric acid and reverse aqua regia is used for leaching the lead smelting solid waste after alkali fusion treatment, the complexation of tartrate radicals to metal ions and the complexation of reverse aqua regia to silver ions are utilized to generate soluble double salts, the reverse aqua regia has good oxidizability, the metal ions can be kept in a high valence state, the complexation of tartaric acid is better facilitated, the problem that the detected liquid obtained by leaching is turbid and hydrolyzed to cause incapability of detection or poor precision is effectively solved, and the interference of non-target elements is eliminated;
the method has the advantages of simple sample treatment, accurate and quick analysis result, and capability of simultaneously measuring the contents of copper, tin and bismuth in the lead smelting solid waste such as soot, alkaline residue, lead anode mud and the like.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic flow diagram of the assay method provided in examples 1-5.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A method for measuring the contents of copper, tin and bismuth in lead smelting solid waste with high silver content comprises the following steps:
carrying out alkali fusion treatment on the lead smelting solid waste to obtain an alkali melt, and leaching the alkali melt by using a mixed solution to obtain a solution to be detected;
measuring the solution to be measured by using an ICP-AES method, and calculating the contents of copper, tin and bismuth in the lead smelting solid waste through a standard solution working curve;
the mixed solution comprises a mixture of tartaric acid and reverse aqua regia, and the mass content of silver in the lead smelting solid waste is 0.5-20%.
Lead smelting solid waste, especially a sample with high silver content, is subjected to alkaline fusion treatment and leaching in a pretreatment process, on one hand, a solution is turbid due to complex components and the formation of insoluble substances, and cannot be effectively measured; on the other hand, due to the existence of Ag, soluble silver salt is difficult to form, and the silver salt is often hydrolyzed into colloid, so that the liquid to be detected is turbid, and effective and accurate determination cannot be realized.
For this purpose, tartaric acid + retro-aqua regia are usedThe mixed solution solves the above problem (when the volume ratio of concentrated hydrochloric acid to concentrated nitric acid is 1: 3, it is called reverse aqua regia). The specific principle is as follows: the tartrate radical can be complexed with the following metal ions: al (Al)3+、Be2+、Bi3+、Cd2+、Co2+、Mo(Ⅵ)、Nb(Ⅴ)、Ni2+、Pd2+、Rh3+、Sb(Ⅲ,Ⅴ)、Sn2+、Sn(Ⅳ)、Ta(Ⅴ)、W(Ⅵ)、Zn2+Etc., but silver is not, whereas reverse aqua regia can solve the problem of Ag hydrolysis.
In an alternative embodiment, the alkali melt processing comprises: and mixing the lead smelting solid waste with sodium peroxide, and heating and melting.
In an optional embodiment, the mass ratio of the lead smelting solid waste to the sodium peroxide is (0.05-0.15): 1.
optionally, the mass ratio of the lead smelting solid waste to the sodium peroxide may be 0.05: 1. 0.10: 1. 0.15: 1 and (0.05-0.15): 1, or any value between.
In an alternative embodiment, the heating temperature is 600 ℃ to 800 ℃ and the molten state holding time is 20min to 40 min.
Optionally, the heating temperature can be 600-800 ℃, and the molten state holding time can be any value between 20min, 30min, 40min and 20min-40 min.
In an alternative embodiment, the mass to volume ratio of tartaric acid to the retro-aqua regia is (0.2-2) g: (25-30) ml.
Although tartaric acid has a certain coordination ability, it cannot complex silver ions, and requires a strong acid for complexing. Because the complex acid of the reverse aqua regia has strong oxidability, the anion of the reverse aqua regia has good coordination property and can generate a plurality of soluble double salts; meanwhile, the reverse aqua regia anion not only has good coordination property and can be complexed with silver to generate soluble double salt, but also has good oxidability, can keep metal ions in a high valence state and is more beneficial to tartaric acid to play a complexing role, so that the tartaric acid and the reverse aqua regia can be used for leaching lead smelting solid waste samples after alkali fusion without hydrolysis.
When the method is used, the contents of all main elements in the lead smelting solid waste can reach: 5-20% of Pb, 0.5-20% of Ag, 0.015-0.8% of Au, 78-21% of Bi2, 25-50% of Sb and 1.5-5% of Cu (anode mud); the caustic sludge mainly contains various elements such as silver, silicon, iron, aluminum, calcium, magnesium, sodium, chlorine, sulfur, carbon and the like; the flue dust mainly contains antimony and lead as elements, and also contains Ag, Cu, Pb, Zn, Al, Ca, Mg, K, Na, Mn, Ti, Ni, Co, Cd and the like. The content of gold, silver and antimony is high, and the samples need to be leached by utilizing the synergistic effect of tartaric acid and reverse aqua regia to dissolve and clarify the samples instead of emulsion state.
The anion in the reverse aqua regia is:
3HNO3 + HCl ==== H2[(N3O8)Cl] ==== [(N3O8)Cl]2- + 2H+。
optionally, the mass-to-volume ratio of the tartaric acid to the retrograde aqua regia may be 0.2 g: 25ml, 0.5 g: 25ml, 1 g: 25ml, 1.5 g: 25ml, 2 g: 25ml, 0.2 g: 30ml, 0.5 g: 30ml, 1 g: 30ml, 1.5 g: 30ml, 2 g: 30ml and (0.2-2) g: (25-30) ml.
In an alternative embodiment, the mass to volume ratio of tartaric acid to the retro-aqua regia is 1 g: (25-30) ml.
Optionally, the mass-to-volume ratio of the tartaric acid to the retrograde aqua regia may be 1 g: 25ml, 1 g: 26ml, 1 g: 27ml, 1 g: 28ml, 1 g: 29ml, 1 g: 30ml and 1 g: (25-30) ml.
In an alternative embodiment, the standard solution working curve is obtained by:
and measuring a plurality of copper, tin and bismuth mixed standard solutions with different concentrations by using an ICP-AES method, and fitting by taking the concentration value as an abscissa and the signal intensity value as an ordinate to obtain a working curve of the standard solution.
In an alternative embodiment, a sample blank solution is added to the mixed standard solution;
the preparation method of the sample blank solution comprises the following steps: and carrying out alkali fusion treatment without adding the lead smelting solid waste, and then leaching by using the mixed solution to obtain the sample blank solution.
In an alternative embodiment, during the measuring, the operating conditions of the inductively coupled plasma emission spectrometer are as follows:
the RF power is 1000W-1200W, the plasma air flow is 15.0L/min, the auxiliary air flow is 1.50L/min, the atomizing air flow is 0.60L/min-0.70L/min, and the observation height is 4mm-8 mm.
Alternatively, the RF power may be any value between 1000W, 1100W, 1200W, and 1000W-1200W; the flow rate of the atomizing gas can be any value between 0.60L/min, 0.65L/min, 0.70L/min and 0.60L/min-0.70L/min; the viewing height may be any value between 4mm, 5mm, 6mm, 7mm, 8mm and 4mm-8 mm.
In an alternative embodiment, during the determination, the wavelengths of the analytical elements are: 327.395nm of copper, 189.925nm of tin and 223.061nm of bismuth.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The apparatus and reagents used in the examples are first described, specifically as follows:
equipment: an inductively coupled plasma spectrometer, model Agilent ICP-OES 725 (Agilent technologies, usa);
reagent: sodium peroxide (analytically pure), tartaric acid (analytically pure), hydrochloric acid (analytically pure), nitric acid (analytically pure), and ultrapure water (self-made); standard stock solutions: standard stock solutions of copper, tin and bismuth were provided by the national institute of iron and steel, except that the concentration of tin was 500. mu.g/mL, the other concentrations were 1000. mu.g/mL.
Examples 1 to 5
5 samples (silver content between 0.5% and 20%) were taken and measured according to the following method (scheme shown in FIG. 1):
(1) and (3) decomposing the sample: accurately weighing 0.2000g of sample, uniformly mixing the sample in a 25mL corundum crucible with about 1g of sodium peroxide at the bottom, covering about 1g of sodium peroxide, placing the corundum crucible in a muffle furnace heated to 700 ℃, keeping the temperature for melting for 20 minutes, taking out the crucible, slightly cooling, placing the crucible in a 250mL beaker containing 5mL of tartaric acid (200 g/L) and 25mL of reverse aqua regia for leaching, washing the crucible with hot 2% hydrochloric acid after the melt is stopped from falling off due to violent action, cooling, transferring the crucible into a 100mL volumetric flask, and adding water to dilute the crucible to a scale. A sample blank solution (without sample, directly melted with sodium peroxide and then leached) was prepared as described above. 5mL of the test solution is divided, placed in a 100mL volumetric flask, added with 10mL of hydrochloric acid, diluted to the scale with water and mixed uniformly.
(2) Preparing a working curve of a standard solution: transferring 0.00, 0.50, 2.00, 4.00, 6.00 mL and 8.00 mL of mixed standard solutions (100 mu g/mL) of copper, tin and bismuth into a 100mL volumetric flask to prepare series of standard working solutions with the concentrations of 0.00, 0.50, 2.00, 4.00, 6.00 and 8.00 mu g/mL, adding 5mL of sample blank solution, adding 10% HCl, diluting to scale, and shaking up.
(3) The instrument is in an optimal state: RF power: 1000W, 15.0L/min of plasma airflow, 1.50L/min of auxiliary airflow, 0.60L/min of atomizing airflow, 6mm of observation height and 5s of reading time, wherein the wavelengths of analytical elements are respectively as follows: 327.395nm of copper, 189.925nm of tin and 223.061nm of bismuth. And starting the ICP, after each index of the instrument meets the requirement and the ignition is stable for half an hour, establishing an analysis method of the sample according to the working condition of the ICP, selecting the optimal wavelength under the optimal instrument condition, sequentially measuring the blank solution, the standard solution and the liquid to be measured, fitting a linear curve by taking the concentration value as an abscissa and the signal intensity value as an ordinate, and calculating the content of copper, tin and bismuth elements.
The reagent blank solution was measured 11 times and the standard deviation was calculated with 3 times the standard deviation as the detection limit and 5 times the detection limit as the lower measurement limit, and the results are shown in table 1.
TABLE 1 lower detection limits for instruments and methods
The results of the precision experiments of examples 1-5 are shown in Table 2:
TABLE 2 results of the precision test
To further illustrate the accuracy of the method, a corresponding sample was selected, a certain amount of standard solution was added, the sample was processed as specified by the standard, and a spiking recovery experiment was performed, with the results shown in table 3.
TABLE 3 test results of recovery with addition of a label
The standard curves respectively corresponding to the copper, tin and bismuth after the elements are measured have good linear relation, and the correlation coefficient is 0.9991-0.9999. The detection limit of the method is 0.010-0.10 g/mL, the precision is less than 2%, the recovery rate is 97.7-102.3%, and the method is high in precision, stable and reliable in measurement result, and capable of rapidly and accurately detecting the contents of copper, tin and bismuth in the ash, the caustic sludge and the lead anode slime.
Wherein, the standard curves respectively corresponding to the copper, tin and bismuth after the determination are shown in the following table 4:
TABLE 4 Standard curves corresponding to the elements respectively
Comparative example 1
Unlike example 1, in the mixed solution, the retro aqua regia was replaced with concentrated hydrochloric acid and concentrated nitric acid at a volume ratio of 1: 1.
Comparative example 2
Unlike example 1, in the mixed solution, the retro aqua regia was replaced with concentrated hydrochloric acid and concentrated nitric acid at a volume ratio of 1: 2, or a mixture thereof.
Comparative example 3
Unlike example 1, in the mixed solution, the retro aqua regia was replaced with concentrated hydrochloric acid and concentrated nitric acid at a volume ratio of 2: 1.
Comparative example 4
Unlike example 1, in the mixed solution, the retro aqua regia was replaced with concentrated hydrochloric acid and concentrated nitric acid at a volume ratio of 3: 1.
Comparative example 5
In contrast to example 1, concentrated hydrochloric acid was used instead of queen bee water in the mixed solution.
Comparative example 6
In contrast to example 1, instead of the reverse aqua regia, concentrated nitric acid was used in the mixed solution.
The results of the solutions tested, obtained by taking 5 samples from examples 1-5 and subjecting them to alkaline fusion treatment and leaching respectively, are shown in Table 5:
TABLE 5 liquid State to be tested
As can be seen from Table 5 above, in the test solution state, the test solutions obtained in examples 1 to 5 by using tartaric acid + retro-aqua regia as the mixed solution are most advantageous for the subsequent measurement. While the protocols provided in comparative examples 1-6 only partially allow for continued subsequent testing.
To better illustrate the effect of tartaric acid on the assay, the amount of tartaric acid was examined as follows:
adding tartaric acid with the same concentration and different volumes, measuring standard solutions of copper, tin and bismuth with the content of 5ug/mL, respectively adding 200g/L tartaric acid solutions of 2mL, 4mL, 6mL, 8mL, 10mL and 12mL into the 5ug/mL solution, wherein the measurement result on the first day is unchanged, when the adding amount of the tartaric acid is 2mL and 4mL after the fourth day, the measurement result is low, other measurement results are stable, which indicates that the concentration of the tartaric acid cannot be too low, but if the adding amount of the tartaric acid is too large, the tartaric acid is a dibasic acid, the tartaric acid reacts with alkali to generate acid salt which is difficult to be dissolved in cold water, so that precipitation is generated, and the atomizer of an instrument is blocked, and the volume of the tartaric acid (200 g/L) is controlled to be 5 mL.
Further quantitative tests were carried out, and the effect of the tartaric acid dosage on the determination of the tin content is shown in table 6 below:
TABLE 6 influence of tartaric acid dosage on the determination of 4.992% tin in the sample
The data in table 6 above show that the use of 5ml or 5.5ml of tartaric acid had minimal effect on the determination of the tin content. For comprehensive consideration, the tartaric acid dosage is finally selected to be 5 ml.
When a sample with high content of antimony, tin, silver and the like is encountered, the sample can be dissolved by acid with higher concentration, the volume fraction of the acid needs to be kept above 25%, but the excessive acidity has influence on an instrument and is not environment-friendly, so that the optimal volume of the retrograde aqua regia is determined by further experiments, namely the mass-to-volume ratio of the tartaric acid to the retrograde aqua regia is 1 g: preferably 25-30 ml.
The specific data are shown in table 7 below:
TABLE 7 Effect of Redox dose on the determination of tin at 3.952% in the sample
The data in Table 7 above show that the most accurate measurement results are obtained when the amount of the reverse aqua regia is 25 ml. Comprehensively considering, the dosage of the reverse aqua regia is 25-30 ml.
To further illustrate the accuracy of the measurement method provided by the present application, the influence of each coexisting element on the detection of the target element is examined, specifically as follows:
1. interference experiment of antimony
Antimony elements with different concentrations are added into the Cu, Sn and Bi standard solutions of 0.50 mug/mL and 8.00 mug/mL respectively, and the measurement results are shown in tables 8 and 9.
TABLE 8 interference test of antimony (1)
TABLE 9 interference test of antimony (2)
Experiments and data in the tables 8 and 9 show that the influence of the coexisting element antimony on the determination of the elements Cu, Sn and Bi to be detected can be ignored.
2. Interference experiment of silver
Silver elements with different concentrations are added into the Cu, Sn and Bi standard solutions of 0.50 mug/mL and 8.00 mug/mL respectively, and the measurement results are shown in tables 10 and 11.
TABLE 10 silver interference experiment (1)
TABLE 11 silver interference experiment (2)
The experiment and the data in tables 10 and 11 show that the influence of the coexisting element silver on the determination of the elements Cu, Sn and Bi to be detected can be ignored.
3. Calcium interference test
Calcium elements with different concentrations are added into the Cu, Sn and Bi standard solutions of 0.50 mug/mL and 8.00 mug/mL respectively, and the measurement results are shown in tables 12 and 13.
TABLE 12 calcium interference test (1)
TABLE 13 calcium interference test (2)
The experiment and the data in tables 12 and 13 show that the determination influence of the coexisting element calcium on the elements Cu, Sn and Bi to be detected can be ignored.
4. Interference test of lead
Lead elements with different concentrations are added into the Cu, Sn and Bi standard solutions of 0.50 mug/mL and 8.00 mug/mL respectively, and the measurement results are shown in tables 14 and 15.
TABLE 14 interference test of lead (1)
TABLE 15 interference test of lead (2)
The data of the experiment and the data in tables 14 and 15 show that the influence of the coexisting element lead on the determination of the elements Cu, Sn and Bi to be detected can be ignored.
5. Interference experiments with sodium
In the experimental method, the flux used for alkali fusion is sodium peroxide, a large amount of sodium ions are introduced into the solution, interference experiments are carried out on Cu, Sn and Bi standard solutions containing 0.50 mug/mL and 8.00 mug/mL by adding sodium elements with different contents, and the measurement results are shown in tables 16 and 17.
TABLE 16 interference experiment of sodium (1)
TABLE 17 interference experiment (2) of sodium
Experiments and data in tables 16 and 17 show that sodium has certain influence on the determination of the elements Cu, Sn and Bi to be detected after the sodium matrix element is added. Therefore, 5mL of sample blank solution was added for matrix matching when preparing the standard curve solution.
6. Interference of mixed elements
20mg of coexisting ions were added to the Cu, Sn, Bi standard solutions of 0.50 μ g/mL and 8.00 μ g/mL, respectively, and the measurement results are shown in Table 18.
TABLE 18 measurement results of mixed ion interference test (unit mg/L)
The experimental results show that: within the tolerance range of +/-5%, under the condition of the ion adding amount, the measurement interference of the coexisting ions on the elements Cu, Sn and Bi to be measured is small.
Comparative examples 7 to 9
The measurement of 50mg/L copper solution by the conventional iodometric titration method, the measurement of 50mg/L tin solution by the potassium iodate titration method, and the measurement of 50mg/L bismuth solution by the EDTA titration method were repeated three times, and the control results are shown in Table 19.
TABLE 19 comparison of different methods
As can be seen from table 19 above, the method provided by the present application has higher measurement accuracy than the conventional method.
Comparative examples 10 to 11
To further demonstrate the synergistic effect between tartaric acid and retro-aqua regia, control experiments were conducted with samples (copper content 2.655%, tin content 3.952%, bismuth content 6.920%) leached using 25ml of retro-aqua regia and 30ml of retro-aqua regia alone and the same samples leached using 5ml of tartaric acid (200 g/L) +25ml of retro-aqua regia and 5ml of tartaric acid (200 g/L) +30ml of retro-aqua regia, respectively, with the measurements shown in table 20 below:
TABLE 20 control test data
As can be seen from the data in Table 20 above, the tartaric acid plus the aqua regia are used as the leaching solution, and the detection result is obviously superior to that of the single use of the aqua regia for leaching.
The method also selects hydrogen peroxide and the retrograde aqua regia to leach, and the detection result of the method is not much different from that of the method of singly using the retrograde aqua regia, so that the scheme of leaching the hydrogen peroxide and the retrograde aqua regia is shown, and the problem of insufficient detection precision exists in the detection of the sample with high silver content.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (5)
1. A method for measuring the contents of copper, tin and bismuth in lead smelting solid waste with high silver content is characterized by comprising the following steps:
carrying out alkali fusion treatment on the lead smelting solid waste to obtain an alkali melt, and leaching the alkali melt by using a mixed solution to obtain a solution to be detected;
measuring the solution to be measured by using an ICP-AES method, and calculating the contents of copper, tin and bismuth in the lead smelting solid waste through a standard solution working curve; the standard solution working curve is obtained by the following method: measuring a plurality of copper, tin and bismuth mixed standard solutions with different concentrations by using an ICP-AES method, and fitting by taking the concentration value as an abscissa and the signal intensity value as an ordinate to obtain a working curve of the standard solution; adding a sample blank solution into the mixed standard solution; the preparation method of the sample blank solution comprises the following steps: performing alkali fusion treatment without adding the lead smelting solid waste, and leaching by using the mixed solution to obtain a sample blank solution; in the measuring process, the working conditions of the inductively coupled plasma emission spectrometer are as follows: the RF power is 1000W-1200W, the plasma air flow is 12.0-18.0L/min, the auxiliary air flow is 0-2.25L/min, the atomizing air flow is 0.60L/min-0.70L/min, and the observation height is 4mm-8 mm; in the measuring process, the wavelengths of the analysis elements are respectively as follows: copper 327.395nm, tin 189.925nm and bismuth 223.061 nm;
the mixed solution comprises a mixture of tartaric acid and reverse aqua regia, and the mass content of silver in the lead smelting solid waste is 0.5-20%; the mass-volume ratio of the tartaric acid to the retrograde aqua regia is (0.2-2) g: (25-30) ml.
2. The assay method according to claim 1, wherein the alkali melt processing comprises: and mixing the lead smelting solid waste with sodium peroxide, and heating and melting.
3. The determination method according to claim 2, wherein the mass ratio of the lead smelting solid waste to the sodium peroxide is (0.05-0.15): 1.
4. the method according to claim 2, wherein the heating temperature is 600 ℃ to 800 ℃ and the molten state holding time is 20min to 40 min.
5. The method according to claim 1, wherein the mass-to-volume ratio of tartaric acid to the retro-aqua regia is 1 g: (25-30) ml.
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