Method for determination of high content of copper, lead and zinc in polymetallic ore and copper-lead-zinc alloy by ICP-AES

Abstract

The present application relates to a method for determining high content copper, lead and zinc in polymetallic ore and copper-lead-zinc alloy by ICP-AES, and belongs to the technical field of ICP-AES analysis and testing, and the specific steps are as follows: the polymetallic ore and copper-lead-zinc alloy sample is decomposed into wet salt by aqua regia; then hydrochloric acid-ammonium acetate mixed extraction liquid is added, and the mixture is heated to micro-boiling for 10-15 min; the extracted sample is diluted with deionized water in a 250 mL volumetric flask; the diluted sample is shaken and left to clarify; 5 mL of supernatant solution is taken out with a 10 mL large-volume pipette and placed in a 50 mL colorimetric tube, 5 mL of hydrochloric acid-ammonium acetate mixed extraction liquid is added, and the mixture is diluted and shaken; the obtained sample is subjected to ICP-AES testing to determine the content of copper, lead and zinc. The present application avoids complicated operation, solves the problem of serious low test results caused by mutual influence of lead, copper and zinc during testing, and can improve the testing accuracy of high content copper, lead and zinc in polymetallic ore and copper-lead-zinc alloy.

Description

Technical Field

[0001] This invention relates to the field of ICP-AES analysis and testing technology, and in particular to a method for determining high copper, lead, and zinc content in polymetallic ores and copper-lead-zinc alloys using ICP-AES. Background Technology

[0002] Currently, the EDTA titration method is used for high-content lead and zinc in polymetallic ores and copper-lead-zinc alloys, while the iodometric method is used for copper. The principle of lead determination is that the sample is decomposed with hydrochloric acid and nitric acid. In the presence of sulfuric acid, lead precipitates as lead sulfate. The filtered lead precipitate is dissolved in an acetate-sodium acetate buffer solution, titrated with EDTA standard solution using xylenol orange as an indicator. The principle of zinc determination is the same: the sample is decomposed with hydrochloric acid and nitric acid. In the presence of sulfate, lead precipitates as lead sulfate. Ammonia is used to adjust the pH, forming a precipitate. Zinc complexes with ammonium ions. Filtration removes interferences such as iron and chromium. The zinc precipitate is then dissolved in an acetate-sodium acetate buffer solution. The solution is prepared in a buffer solution, with xylenol orange as an indicator, and titrated with EDTA standard solution. However, copper ions cannot be separated in this process, and a large number of copper ions cannot be masked, interfering with the determination of zinc. In the determination of copper, the principle is that the sample is decomposed with hydrochloric acid and nitric acid, and copper exists in the form of copper sulfate under sulfuric acid fuming treatment. After water extraction, divalent copper ions react with potassium iodide in a buffer solution to produce elemental iodine. Starch is used as an indicator, and titration is performed with sodium thiosulfate standard solution. In this process, if a large amount of lead exists in the form of lead sulfate precipitate, it will seriously affect the determination of the titration endpoint and make it impossible to accurately determine the copper content in polymetallic ores and copper-lead-zinc alloys.

[0003] Traditional testing methods have the following shortcomings: First, the analysis cycle is long, and copper, lead, and zinc in polymetallic ores and copper-lead-zinc alloys need to be tested separately; second, when the content of copper, lead, and zinc in polymetallic ores and copper-lead-zinc alloys is high, copper affects the determination of zinc, and lead affects the determination of copper, often making it impossible to accurately determine the content of copper, lead, and zinc in polymetallic ores and copper-lead-zinc alloys; third, there are many influencing factors. Due to the long analysis cycle and many steps, the analysts must be experienced and technically proficient. Any oversight in any step will distort the test results, and the accuracy of the results cannot be guaranteed. Summary of the Invention

[0004] To overcome the problems existing in the background technology, the present invention provides a method for determining high copper, lead and zinc content in polymetallic ores and copper-lead-zinc alloys using ICP-AES. This method avoids cumbersome operations, solves the problem of lead, copper and zinc interfering with each other during testing, resulting in seriously low test results, and can improve the testing accuracy of high copper, lead and zinc content in polymetallic ores and copper-lead-zinc alloys.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] The specific steps for determining high copper, lead, and zinc content in polymetallic ores and copper-lead-zinc alloys using ICP-AES are as follows:

[0007] 1) Polymetallic minerals and copper-lead-zinc alloy samples were decomposed into wet salt form using aqua regia;

[0008] 2) Add hydrochloric acid-ammonium acetate mixed extraction solution to the wet salt sample after decomposition with aqua regia, and heat to a gentle boil for 10-15 minutes;

[0009] 3) Dilute the extracted sample in a 250 mL volumetric flask with deionized water;

[0010] 4) Shake the sample after adjusting the volume and let it clarify;

[0011] 5) Use a 10mL large pipette to transfer 5mL of the supernatant solution from step 4) into a 50mL colorimetric tube, add 5mL of hydrochloric acid-ammonium acetate mixed extraction solution, make up to volume and shake well;

[0012] 6) Perform ICP-AES testing on the sample obtained in step 5) to determine the content of copper, lead and zinc.

[0013] Preferably, in step 1), the ratio of aqua regia used is 0.05g to 0.5g: 20mL.

[0014] Preferably, in step 2), the medium of the hydrochloric acid-ammonium acetate mixed extraction solution is 1+1 hydrochloric acid, the concentration of ammonium acetate is 200g / L, and the usage ratio of the hydrochloric acid-ammonium acetate mixed extraction solution is 0.05g~0.5g:50mL.

[0015] Further, in step 6), the ICP-AES test conditions are as follows: high frequency generator power 1.15KW; analysis pump speed 50rpm; stabilization time 15s; auxiliary gas flow rate 0.5L / min; vertical observation height 12.0mm; copper analytical line 324.75nm; lead analytical line 220.35nm; zinc analytical line 213.86nm.

[0016] Furthermore, the preparation of the ICP-AES standard working curve for ICP-AES testing is as follows: Take 0.00 mL, 0.50 mL, 5.00 mL, 10.00 mL, 20.00 mL, and 40.00 mL of a 1000 μg / mL copper-lead-zinc mixed standard solution and place them in a set of 100 mL volumetric flasks. Add 10 mL of hydrochloric acid-ammonium acetate mixed extraction solution, dilute to the mark with deionized water, and shake well.

[0017] The beneficial effects of this invention are as follows: When processing polymetallic minerals and copper-lead-zinc alloy samples, this invention adds a certain amount of ammonium acetate for treatment, which can solve the problem of severely low test results caused by the mutual influence of high lead, copper, and zinc ion contents. It can improve the test accuracy of high copper, lead, and zinc contents in polymetallic minerals and copper-lead-zinc alloys. In addition, it can also simultaneously analyze the contents of major and minor elements such as chromium, cadmium, nickel, cobalt, iron, and manganese in polymetallic minerals and copper-lead-zinc alloy samples. Detailed Implementation

[0018] Example 1

[0019] Weigh 0.1000g of a polymetallic ore sample (copper, lead, and zinc contents of 9.13%, 29.62%, and 17.56%, respectively), place it in a 100mL beaker, moisten it with a little water, and then decompose it with aqua regia until it reaches a wet salt state. The ratio of polymetallic ore sample to aqua regia is 0.1g:20mL. Add a hydrochloric acid-ammonium acetate mixed extraction solution to the wet salt state sample after aqua regia decomposition. The medium for the hydrochloric acid-ammonium acetate mixed extraction solution is 1+1 hydrochloric acid, and the concentration of ammonium acetate is 2%. 0.00 g / L, using a ratio of 0.05 g: 50 mL, heat to a gentle boil for 10–15 min; dilute the polymetallic mineral sample to volume with deionized water in a 250 mL volumetric flask; shake the diluted sample well and let it clarify; use a 10 mL large-diameter pipette to transfer 5 mL of the supernatant solution into a 50 mL colorimetric tube, add 5 mL of hydrochloric acid-ammonium acetate mixed extraction solution, dilute to volume and shake well; perform ICP-AES testing on the obtained sample to determine the copper, lead, and zinc content.

[0020] Preparation of ICP-AES standard working curve: Take 0.00 mL, 0.50 mL, 5.00 mL, 10.00 mL, 20.00 mL, and 40.00 mL of a 1000 μg / mL copper-lead-zinc mixed standard solution and place them in a set of 100 mL volumetric flasks. Add 10 mL of hydrochloric acid-ammonium acetate mixed extraction solution, dilute to the mark with deionized water, shake well, and wait for the test.

[0021] The ICP-AES test conditions were as follows: high-frequency generator power 1.15KW; analytical pump speed 50rpm; stabilization time 15s; auxiliary gas flow rate 1.2L / min; nebulizer flow rate 0.5L / min; vertical observation height 12.0mm; copper analytical line 324.75nm; lead analytical line 220.35nm; zinc analytical line 213.86nm.

[0022] Example 2

[0023] Weigh 0.0500 g of a copper-lead-zinc alloy sample (copper, lead, and zinc contents of 15.32%, 24.37%, and 39.22%, respectively), place it in a 100 mL beaker, moisten it with a small amount of water, and then decompose it with aqua regia until it reaches a wet salt state. The ratio of polymetallic mineral sample to aqua regia is 0.5 g: 20 mL. Add a hydrochloric acid-ammonium acetate mixed extraction solution to the wet salt state sample after aqua regia decomposition. The medium for the hydrochloric acid-ammonium acetate mixed extraction solution is 1+1 hydrochloric acid, and the concentration of ammonium acetate is [missing information]. 200 g / L, using a ratio of 0.5 g: 50 mL, heat to a gentle boil for 10–15 min; dilute the treated polymetallic mineral sample to volume with deionized water in a 250 mL volumetric flask; shake the diluted sample well and let it clarify; use a 10 mL large-diameter pipette to transfer 5 mL of the supernatant solution into a 50 mL colorimetric tube, add 5 mL of hydrochloric acid-ammonium acetate mixed extraction solution, dilute to volume and shake well; perform ICP-AES testing on the obtained sample to determine the copper, lead, and zinc content.

[0024] Preparation of ICP-AES standard working curve: Take 0.00 mL, 0.50 mL, 5.00 mL, 10.00 mL, 20.00 mL, and 40.00 mL of a 1000 μg / mL copper-lead-zinc mixed standard solution and place them in a set of 100 mL volumetric flasks. Add 10 mL of hydrochloric acid-ammonium acetate mixed extraction solution, dilute to the mark with deionized water, shake well, and wait for the test.

[0025] The ICP-AES test conditions were as follows: high-frequency generator power 1.15KW; analytical pump speed 50rpm; stabilization time 15s; auxiliary gas flow rate 1.2L / min; nebulizer flow rate 0.5L / min; vertical observation height 12.0mm; copper analytical line 324.75nm; lead analytical line 220.35nm; zinc analytical line 213.86nm.

[0026] Comparative Example 1

[0027] Weigh 0.1000 g of a polymetallic ore sample (copper, lead, and zinc contents of 9.13%, 29.62%, and 17.56%, respectively), place it in a 100 mL beaker, moisten it with a little water, and then decompose it with aqua regia. The ratio of polymetallic ore sample to aqua regia is 0.1 g: 20 mL. Dilute the polymetallic ore sample to volume with deionized water in a 250 mL volumetric flask. Shake the diluted sample well and let it clarify. Use a 10 mL large-diameter pipette to transfer 5 mL of the supernatant solution to a 50 mL colorimetric tube, add deionized water to volume and shake well. Perform ICP-AES testing on the obtained sample to determine the copper, lead, and zinc contents.

[0028] Preparation of ICP-AES standard working curve: Take 0.00 mL, 0.50 mL, 5.00 mL, 10.00 mL, 20.00 mL, and 40.00 mL of a mixed standard solution of copper, lead, and zinc with a concentration of 1000 μg / mL, and place them in a set of 100 mL volumetric flasks. Dilute to the mark with deionized water, shake well, and prepare for testing.

[0029] The ICP-AES test conditions were as follows: high-frequency generator power 1.15KW; analytical pump speed 50rpm; stabilization time 15s; auxiliary gas flow rate 1.2L / min; nebulizer flow rate 0.5L / min; vertical observation height 12.0mm; copper analytical line 324.75nm; lead analytical line 220.35nm; zinc analytical line 213.86nm.

[0030] Comparative Example 2

[0031] Weigh 0.0500 g of a copper-lead-zinc alloy sample (copper, lead, and zinc contents of 15.32%, 24.37%, and 39.22%, respectively), place it in a 100 mL beaker, moisten it with a little water, and then decompose it with aqua regia until it reaches a wet salt state. The ratio of polymetallic mineral sample to aqua regia is 0.5 g: 20 mL. Dilute the sample to volume with deionized water in a 250 mL volumetric flask. Shake the diluted sample well and let it clarify. Use a 10 mL large-diameter pipette to transfer 5 mL of the supernatant solution into a 50 mL colorimetric tube, add deionized water to dilute to volume and shake well. Perform ICP-AES testing on the obtained sample to determine the copper, lead, and zinc contents.

[0032] Preparation of ICP-AES standard working curve: Take 0.00 mL, 0.50 mL, 5.00 mL, 10.00 mL, 20.00 mL, and 40.00 mL of a mixed standard solution of copper, lead, and zinc with a concentration of 1000 μg / mL, and place them in a set of 100 mL volumetric flasks. Dilute to the mark with deionized water, shake well, and prepare for testing.

[0033] The ICP-AES test conditions were as follows: high-frequency generator power 1.15KW; analytical pump speed 50rpm; stabilization time 15s; auxiliary gas flow rate 1.2L / min; nebulizer flow rate 0.5L / min; vertical observation height 12.0mm; copper analytical line 324.75nm; lead analytical line 220.35nm; zinc analytical line 213.86nm.

[0034] The test results of the embodiments and comparative examples of the present invention are shown in Table 1:

[0035] Table 1 Comparison of test results for each embodiment and comparative example

[0036]

[0037] Note: The above is a statistical analysis of the test results of 6 parallel samples.

[0038] As can be seen from Table 1, the test results of the test samples in Examples 1 and 2 are basically the same as the reference values, with small relative errors and high accuracy and precision. Comparative Examples 1 and 2 are existing ICP-AES test methods that do not use hydrochloric acid-ammonium acetate. Their test results show deviations from the reference values, with larger precision and relative errors.

[0039] This invention, when processing high-content copper-lead-zinc polymetallic ores and copper-lead-zinc alloy samples, adds a certain amount of ammonium acetate for treatment. This allows high-content lead to form stable complexes with acetate ions, and copper and zinc to form stable complexes with ammonium ions. This solves the problem of severely low test results caused by mutual interference when the content of lead, copper, and zinc ions is high. It can improve the testing accuracy of high-content copper, lead, and zinc in polymetallic ores and copper-lead-zinc alloys. In addition, it can also simultaneously analyze the content of major and minor elements such as chromium, cadmium, nickel, cobalt, iron, and manganese in polymetallic ores and copper-lead-zinc alloy samples.

[0040] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. A method for determining high content of copper, lead and zinc in polymetallic ores and copper-lead-zinc alloys by ICP-AES, characterized in that, The specific steps are: 1) The multi-metal ore and copper-lead-zinc alloy sample is decomposed into wet salt by aqua regia, and the use ratio of aqua regia is 0.05g-0.5g:20mL; 2) The wet salt sample after aqua regia decomposition is added with hydrochloric acid-ammonium acetate mixed extraction liquid, and heated to micro-boiling for 10-15min, the medium of the hydrochloric acid-ammonium acetate mixed extraction liquid is 1+1 hydrochloric acid, the concentration of ammonium acetate is 200g / L, and the use ratio of the hydrochloric acid-ammonium acetate mixed extraction liquid is 0.05g-0.5g:50mL; 3) The sample after extraction in step 2) is constant volume in a 250mL volumetric flask with deionized water; 4) The constant volume sample is shaken and clarified; 5) 5mL of supernatant solution in step 4) is taken out with a 10mL graduated pipette into a 50mL colorimetric tube, 5mL of hydrochloric acid-ammonium acetate mixed extraction liquid is added, constant volume and shaking; 6) The sample obtained in step 5) is tested by ICP-AES to determine the copper, lead and zinc content.

2. The method for determining high content of copper, lead and zinc in polymetallic ore and copper-lead-zinc alloy by ICP-AES according to claim 1, characterized in that: In step 6), the ICP-AES test conditions are: high frequency generator power 1.15KW; analysis pump speed 50rpm; stabilization time 15s; auxiliary gas flow 0.5L / min; vertical observation height 12.0mm; copper analysis spectral line 324.75nm; lead analysis spectral line 220.35nm; zinc analysis spectral line 213.86nm.

3. The method for determining high content of copper, lead and zinc in polymetallic ore and copper-lead-zinc alloy by ICP-AES according to claim 1, characterized in that: The preparation of ICP-AES standard working curve for ICP-AES test: 0.00mL, 0.50mL, 5.00mL, 10.00mL, 20.00mL and 40.00mL of copper-lead-zinc mixed standard solution with a concentration of 1000μg / mL are respectively placed in a group of 100mL volumetric flasks, 10mL of hydrochloric acid-ammonium acetate mixed extraction liquid is added, diluted to the mark with deionized water, and shaken.

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