CN114526974B - Method for dissolving insoluble noble metal sample - Google Patents
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- CN114526974B CN114526974B CN202210254724.3A CN202210254724A CN114526974B CN 114526974 B CN114526974 B CN 114526974B CN 202210254724 A CN202210254724 A CN 202210254724A CN 114526974 B CN114526974 B CN 114526974B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
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- G—PHYSICS
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- G01N1/38—Diluting, dispersing or mixing samples
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- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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Abstract
The invention relates to a dissolving technology of a noble metal sample, in particular to a dissolving method of a difficult-to-dissolve noble metal sample. According to the method, a high-purity tin foil is used for wrapping a non-soluble noble metal sample, the temperature is increased to 400-450 ℃ at a constant speed in a hydrogen atmosphere and is kept for 0.5-1 h, then the temperature is increased to 800-850 ℃ at a constant speed and is kept for 1-2 h, heating is stopped, and the temperature is cooled to room temperature in a hydrogen reducing atmosphere to obtain a tin alloy molten bead; adding hydrochloric acid and hydrogen peroxide into the tin alloy molten beads, sealing, then placing at 155-170 ℃ for heat preservation for 24-48 h, and cooling at room temperature to obtain a solution A; boiling the solution A to remove chlorine, cooling to obtain a solution B, and adding the solution B into dilute hydrochloric acid to be used as a solution to be tested. According to the invention, the noble metal rhodium, ruthenium, iridium and the like can generate intermetallic compounds with the active metal tin under a high-temperature reducing atmosphere, and can be completely dissolved under the conditions of chlorination, heating and pressurization, so that the technical defect of the traditional sample containing the noble metal rhodium, ruthenium and iridium in dissolution is overcome, the operation process is simple, and the purpose of completely dissolving the noble metal elements can be achieved.
Description
Technical Field
The invention relates to a dissolving technology of a noble metal sample, in particular to a dissolving method of a difficult-to-dissolve noble metal sample.
Background
Noble metals are mainly used in the manufacture of important key materials in modern high-tech fields, such as: rhodium can be used for preparing high-temperature thermocouple temperature-measuring alloy materials, ruthenium can be used for preparing sputtering ruthenium targets widely used in semiconductor production, and iridium can be used for preparing crucible materials for controlling high-purity single crystal growth.
The noble metal has high ionization potential and strong chemical stability, has high corrosion resistance to a plurality of chemical reagents at normal temperature, particularly rhodium, ruthenium and iridium, has the strongest corrosion resistance to acid in difficult soluble metal even under the condition of heating, is insoluble in any acid under normal conditions, and is slightly soluble in aqua regia only under the condition of heating. Therefore, when a sample containing insoluble rhodium, ruthenium and iridium is analyzed and detected, sample decomposition is one of the difficulties in analytical chemistry, even if the sample weighing amount is only dozens of milligrams, the sample cannot be completely dissolved by acid under normal conditions, so that the biggest bottleneck of the related analysis method is the dissolution pretreatment technology of the sample, and the key point for meeting the requirement on the accuracy of the analysis result of the insoluble noble metal sample is also achieved.
Disclosure of Invention
Aiming at the problem of dissolving a difficult-to-dissolve noble metal sample in the prior art, the invention provides a method for dissolving the difficult-to-dissolve noble metal sample, namely noble metal rhodium, ruthenium, iridium and the like can generate intermetallic compounds with active metal tin under the high-temperature reducing atmosphere, and the intermetallic compounds can be completely dissolved under the conditions of chlorination, heating and pressurization, so that the technical defect of the traditional sample containing the noble metal rhodium, ruthenium and iridium in dissolving is overcome, the operation process is simple, and the aim of completely dissolving noble metal elements can be fulfilled.
A dissolving method of a difficult-to-dissolve noble metal sample comprises the following specific steps:
(1) wrapping a non-soluble noble metal sample by using a high-purity tin foil, uniformly heating to 400-450 ℃ in a hydrogen atmosphere, keeping the temperature for 0.5-1 h, uniformly heating to 800-850 ℃ and keeping the temperature for 1-2 h, stopping heating, and cooling to room temperature in a hydrogen reducing atmosphere to obtain a tin alloy molten bead;
(2) adding hydrochloric acid and hydrogen peroxide into the tin alloy molten beads obtained in the step (1), sealing, then placing at 155-170 ℃ for heat preservation for 24-48 h, and cooling at room temperature to obtain a solution A;
(3) boiling the solution A to remove chlorine, cooling to obtain a solution B, and adding the solution B into dilute hydrochloric acid to be used as a solution to be tested.
The insoluble noble metal sample in the step (1) contains one or more of rhodium, ruthenium and iridium.
The mass ratio of the insoluble noble metal sample to the high-purity tin foil in the step (1) is 1: 3-5.
The volume ratio of the hydrochloric acid and the hydrogen peroxide in the step (2) is 3-5: 1, wherein the hydrochloric acid is commercially available analytically pure hydrochloric acid.
The volume ratio of the dilute hydrochloric acid in the step (3) to water in preparation is 1: 8-9.
The invention has the beneficial effects that:
(1) the method utilizes insoluble noble metals such as rhodium, ruthenium and iridium to generate intermetallic compound alloy molten beads with high-purity metal tin after being heated at high temperature in the atmosphere of hydrogen reduction, and the molten beads react with hydrochloric acid and hydrogen peroxide under closed hot pressing to generate stable chloro complex coordination compounds so as to achieve the purpose of completely dissolving noble metal samples;
(2) in the dissolving process, only the instrument container made of quartz and polytetrafluoroethylene materials can be adopted, the operation is simple, the cost is low, the safety and the explosion risk are realized, the used reagents are only metallic tin, hydrochloric acid and hydrogen peroxide, the stability of the obtained acidic medium test solution is good, the subsequent determination is facilitated, the smooth operation of the analysis process is ensured, and the dissolution of the batch of the precious metal sample containing difficult-to-dissolve can be realized.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the method for dissolving the insoluble noble metal pure iridium powder sample comprises the following specific steps:
(1) weighing 106.53mg of a pure metal iridium powder sample with the iridium mass fraction not less than 99.9%, placing the sample in a small cup made of high-purity tin foil, wherein the mass fraction of pure tin is 0.43g, the mass ratio of the sample to the high-purity tin is 1:4, drawing and pinching an upper opening by using forceps, placing the sample in a quartz boat, placing the quartz boat in a tubular electric furnace, introducing hydrogen, heating to 400 ℃ from room temperature for 0.5h, continuing to heat to 850 ℃ and keeping the temperature for 2h, continuing to cool the introduced hydrogen to room temperature after power failure, and taking out to obtain alloy molten beads;
(2) placing the alloy molten beads in a polytetrafluoroethylene tank with the volume of 30mL, adding 20mL of commercially available super-grade pure hydrochloric acid and 5mL of super-grade pure hydrogen peroxide, and covering a tank cover for sealing;
(3) heating the sealed polytetrafluoroethylene tank at 165 ℃ and keeping the temperature for 48 hours;
(4) taking out the polytetrafluoroethylene tank, cooling for 3 hours at room temperature, unscrewing the tank cover in a ventilation cabinet, pouring the solution into a beaker, cleaning the inner wall of the tank by pure water, merging washing water into the beaker to obtain a solution A, covering a watch glass, boiling to remove chlorine, cooling to obtain a solution B, and adding the solution B into dilute hydrochloric acid prepared by the volume ratio of hydrochloric acid (commercially available analytically pure hydrochloric acid) to water of 1:9 to be used as a liquid to be tested;
the solution of this example was clear, without residue, and completely dissolved.
Example 2: the dissolving method of the insoluble noble metal iridium-rhodium alloy sample comprises the following specific steps:
(1) cutting a filament metal iridium-rhodium alloy sample containing 90% of iridium by mass into chips, weighing 103.18mg of iridium-rhodium alloy sample chips, placing the chip in a small cup made of high-purity tin foil, keeping the pure tin at 0.36g, keeping the mass ratio of the sample to the high-purity tin at 1:3.5, closing and pinching an upper opening by using a pair of tweezers, placing the chip in a quartz boat, placing the quartz boat in a tubular electric furnace, introducing hydrogen, heating to 420 ℃ from room temperature, keeping the temperature for 0.5h, continuing to heat to 800 ℃ and keeping the temperature for 2h, continuing to cool the hydrogen to room temperature after power failure, and taking out to obtain alloy molten beads;
(2) placing the alloy molten beads in a polytetrafluoroethylene tank with the volume of 30mL, adding 15mL of commercially available analytically pure hydrochloric acid and 3mL of analytically pure hydrogen peroxide, and covering a tank cover for sealing;
(3) heating the sealed polytetrafluoroethylene tank at the temperature of 160 ℃ and keeping the temperature for 24 hours;
(4) taking out the polytetrafluoroethylene tank, cooling for 2.5h at room temperature, unscrewing the tank cover in a ventilation cabinet, pouring the solution into a beaker, cleaning the inner wall of the tank by pure water, merging washing water into the beaker to obtain a solution A, covering a watch glass, boiling to remove chlorine, cooling to obtain a solution B, and adding the solution B into diluted hydrochloric acid prepared by hydrochloric acid (commercially available analytically pure hydrochloric acid) and water in a volume ratio of 1:8.5 to be used as a liquid to be tested;
the solution in the embodiment is clear and has no slag, and is completely dissolved; and then, measuring the contents of iridium and rhodium by using a ferrous sulfate current titration method and an inductively coupled plasma emission spectrometry (ICP-AES) method respectively.
Example 3: the method for dissolving the platinum-palladium-rhodium-iridium-ruthenium-contained waste sample as the secondary resource comprises the following specific steps:
(1) weighing 127.43mg of a secondary resource platinum-palladium-rhodium-iridium-ruthenium-containing waste sample, placing the sample in a small cup made of high-purity tin foil, wherein the mass ratio of pure tin to high-purity tin is 1:3, drawing and pinching an upper opening by using forceps, placing the sample in a quartz boat, placing the quartz boat in a tubular electric furnace, introducing hydrogen, heating to 450 ℃ from room temperature, keeping the temperature for 1h, continuing to heat to 825 ℃ and keeping the temperature for 1h, continuing to cool the introduced hydrogen to room temperature after power failure, and taking out to obtain alloy molten beads;
(2) placing the alloy molten beads in a polytetrafluoroethylene tank with the volume of 30mL, adding 15mL of commercially available analytically pure hydrochloric acid and 3.5mL of analytically pure hydrogen peroxide, and covering a tank cover for sealing;
(3) heating the sealed polytetrafluoroethylene tank at the temperature of 162 ℃ and keeping the temperature for 25 hours;
(4) taking out the polytetrafluoroethylene tank, cooling for 2 hours at room temperature, unscrewing a tank cover in a ventilation cabinet, pouring the solution into a beaker, cleaning the inner wall of the tank by pure water, combining washing water into the beaker to obtain a solution A, covering a surface dish, boiling to remove chlorine, cooling to obtain a solution B, and adding the solution B into diluted hydrochloric acid prepared by hydrochloric acid (commercially available analytically pure hydrochloric acid) and water in a volume ratio of 1:8 to obtain a solution to be tested;
after the solution is stood, the upper liquid is clear, a little acidic white insoluble slag exists at the bottom, and the insoluble slag is proved to be mainly silicon dioxide and contain non-noble metal oxides of titanium, zirconium and the like through analysis methods such as X-ray fluorescence spectrum, fire test gold and the like, but does not contain noble metal elements; the contents of platinum, palladium, rhodium, iridium and ruthenium can be measured by inductively coupled plasma emission spectrometry (ICP-AES).
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A dissolving method of a difficult-to-dissolve noble metal sample is characterized by comprising the following specific steps:
(1) wrapping a high-purity tin foil with a non-soluble noble metal sample, uniformly heating to 400-450 ℃ in a hydrogen atmosphere, keeping the temperature for 0.5-1 h, uniformly heating to 800-850 ℃ and keeping the temperature for 1-2 h, stopping heating, and cooling to room temperature in a hydrogen reducing atmosphere to obtain tin alloy molten beads;
(2) adding hydrochloric acid and hydrogen peroxide into the tin alloy molten beads obtained in the step (1), sealing, then placing at 155-170 ℃ for heat preservation for 24-48 h, and cooling at room temperature to obtain a solution A;
(3) boiling the solution A to remove chlorine, cooling to obtain a solution B, and adding the solution B into dilute hydrochloric acid to be used as a solution to be tested.
2. The method for dissolving a refractory noble metal specimen according to claim 1, wherein: the insoluble noble metal sample in the step (1) contains one or more of rhodium, ruthenium and iridium.
3. The method for dissolving a refractory noble metal specimen according to claim 2, wherein: the mass ratio of the insoluble noble metal sample to the high-purity tin foil in the step (1) is 1: 3-5.
4. The method for dissolving a refractory noble metal specimen according to claim 1, wherein: the volume ratio of the hydrochloric acid to the hydrogen peroxide in the step (2) is 3-5: 1.
5. The method for dissolving a refractory noble metal specimen according to claim 1, wherein: the volume ratio of the hydrochloric acid to the water in the preparation of the dilute hydrochloric acid in the step (3) is 1: 8-9.
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| CN202210254724.3A CN114526974B (en) | 2022-03-15 | 2022-03-15 | Method for dissolving insoluble noble metal sample |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960549A (en) * | 1973-12-07 | 1976-06-01 | Matthey Rustenburg Refiners, Limited | Process for the separation and purification of platinum, rhodium and iridium |
| CN102796864A (en) * | 2012-08-27 | 2012-11-28 | 昆明贵金属研究所 | Method for activating and dissolving insoluble noble metal rhodium |
| JP2018141232A (en) * | 2017-02-27 | 2018-09-13 | 国立大学法人京都大学 | Solid dissolution nanoparticle and method for producing the same, and catalyst |
| CN111304457A (en) * | 2020-03-20 | 2020-06-19 | 康纳新型材料(杭州)有限公司 | Efficient activation dissolving method for rhodium powder |
-
2022
- 2022-03-15 CN CN202210254724.3A patent/CN114526974B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960549A (en) * | 1973-12-07 | 1976-06-01 | Matthey Rustenburg Refiners, Limited | Process for the separation and purification of platinum, rhodium and iridium |
| CN102796864A (en) * | 2012-08-27 | 2012-11-28 | 昆明贵金属研究所 | Method for activating and dissolving insoluble noble metal rhodium |
| JP2018141232A (en) * | 2017-02-27 | 2018-09-13 | 国立大学法人京都大学 | Solid dissolution nanoparticle and method for producing the same, and catalyst |
| CN111304457A (en) * | 2020-03-20 | 2020-06-19 | 康纳新型材料(杭州)有限公司 | Efficient activation dissolving method for rhodium powder |
Non-Patent Citations (2)
| Title |
|---|
| Dissolution of precious metals in supercritical carbon dioxide;Joanna Shaofen Wang 等;《Industrial and Engineering Chemistry Research》;20051231;第44卷(第4期);第922-926页 * |
| 贵金属物料的溶解技术及进展;刘杨 等;《贵金属》;20131130;第34卷(第4期);第65-72页 * |
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