Ruthenium refining device and method

Abstract

The invention relates to the technical field of metal refining, in particular to a ruthenium refining device and method.The ruthenium refining device comprises a distillation system, an absorption system, a reduction filtering system and a vacuum system, the distillation system, the absorption system and the reduction filtering system communicate in sequence, and the vacuum system communicates with the tail end of the absorption system and the reduction filtering system; the ruthenium-containing material reacts with an oxidizing agent in the distillation system to generate ruthenium tetroxide gas; hydrochloric acid in the absorption system is used for absorbing ruthenium tetroxide gas to generate a chlororuthenium acid solution; and the reduction filtering system is used for reducing the chlororuthenium acid in the chlororuthenium acid solution into a ruthenium metal simple substance. In the application, through the cooperation of the distillation system, the absorption system, the reduction filtration system and the vacuum system, the operation process of the concentrated ruthenium is simplified, and the recovery rate of ruthenium metal is improved.

Description

Technical Field

[0001] This application relates to the field of metal refining technology, and in particular to a ruthenium refining apparatus and method. Background Technology

[0002] Ruthenium metal possesses high catalytic activity, high temperature resistance, corrosion resistance, and stable electronic properties, making it widely used in strategic fields such as new energy, high-end manufacturing, and electronic semiconductors. However, ruthenium metal is scarce and highly dispersed in the Earth's crust, making its mining and refining extremely difficult and costly. Therefore, utilizing refining technologies to recover ruthenium metal from ruthenium-containing materials offers a lower-cost and more environmentally friendly way to obtain ruthenium, enabling the sustainable use of ruthenium resources and supporting the development of new energy and high-end manufacturing industries.

[0003] In existing technologies, oxidative distillation can be used to refine ruthenium metal. This involves placing ruthenium-containing materials and an oxidizing agent into a distillation flask, heating the flask with a resistance furnace to convert the ruthenium element in the materials into ruthenium tetroxide gas, which is then separated. The evaporated ruthenium tetroxide gas reacts with a hydrochloric acid absorption solution to generate a chlororuthenium acid solution. This chlororuthenium acid solution is then transferred to a reduction process for reduction, thereby obtaining the ruthenium metal product.

[0004] However, existing ruthenium refining facilities involve cumbersome operating procedures and require a high level of expertise from both the process control personnel and the operators. Furthermore, the overall recovery rate of ruthenium metal is low, making it difficult to meet the demands of large-scale production. Summary of the Invention

[0005] To simplify the operation of ruthenium refining equipment and improve the recovery rate of ruthenium metal, this application provides a ruthenium refining equipment and method.

[0006] This application provides a ruthenium refining apparatus and method, which adopts the following technical solution: A ruthenium refining apparatus includes a distillation system, an absorption system, a reduction filtration system, and a vacuum system. The distillation system, the absorption system, and the reduction filtration system are sequentially connected. The vacuum system is connected to the end of the absorption system and the reduction filtration system. Ruthenium-containing material reacts with an oxidant in the distillation system to generate ruthenium tetroxide gas. The absorption system includes a hydrochloric acid absorption bottle, a third reagent bottle, and a first buffer bottle. The third reagent bottle contains hydrochloric acid and is connected to the hydrochloric acid absorption bottle. Several hydrochloric acid absorption bottles are connected in series to form a multi-stage hydrochloric acid absorption system. The first-stage hydrochloric acid absorption bottle is connected to the distillation system, and the final-stage hydrochloric acid absorption bottle is connected to the vacuum system. The system is interconnected, and the hydrochloric acid in the hydrochloric acid absorption bottle reacts with ruthenium tetroxide gas to generate chlororuthenium acid solution. The inlet of the first buffer bottle is individually connected to several hydrochloric acid absorption bottles, and the outlet of the first buffer bottle is also individually connected to several hydrochloric acid absorption bottles. After the chlororuthenium acid solution in the first-stage hydrochloric acid absorption bottle is transported to the reduction filtration system, the solution in the next-stage hydrochloric acid absorption bottle is transported to the first buffer bottle. The first buffer bottle then transports the solution from the next-stage hydrochloric acid absorption bottle to the previous-stage hydrochloric acid absorption bottle, and so on, transferring the solution from the next-stage hydrochloric acid absorption bottle to the previous-stage hydrochloric acid absorption bottle. The reduction filtration system reduces the chlororuthenium acid in the chlororuthenium acid solution to elemental ruthenium.

[0007] By adopting the above technical solution, the hydrochloric acid in the multi-stage hydrochloric acid absorption bottle is used to absorb ruthenium tetroxide gas, generating a chlororuthenium acid solution. After absorbing ruthenium tetroxide gas, the hydrochloric acid in the first-stage hydrochloric acid absorption bottle is converted into a high-concentration chlororuthenium acid solution, while the subsequent hydrochloric acid absorption bottles contain a low-concentration ruthenium salt solution. After the solution in the first-stage hydrochloric acid absorption bottle is transferred to the reduction filtration system, the solution in the subsequent-stage hydrochloric acid absorption bottle is sequentially transferred to the previous-stage hydrochloric acid absorption bottle, thereby achieving a step-by-step concentration replenishment of the hydrochloric acid absorbent within the absorption bottles. Simultaneously, through the transfer of solutions within the multi-stage hydrochloric acid absorption bottles, the chlororuthenium acid concentration in the secondary-stage absorption bottles is maintained at a low level, which is beneficial for the solution in that stage to fully absorb the ruthenium tetroxide gas escaping from the previous stage. Therefore, through the above operation, the hydrochloric acid absorbent resources can be fully utilized, the absorption rate of ruthenium tetroxide gas can be improved, ruthenium resource waste can be avoided, and the recovery rate of ruthenium metal can be increased.

[0008] Optionally, the distillation system includes a ruthenium distillation fuze, a first reagent bottle, a second reagent bottle, a distillation kettle, a hot water washing bottle, and a cold water washing bottle; the first reagent bottle contains an oxidant, the second reagent bottle contains an acidic solution, the distillation kettle is placed inside the ruthenium distillation fuze, the ruthenium-containing material is placed in the distillation kettle, the first reagent bottle supplies the oxidant to the distillation kettle, the second reagent bottle supplies the acidic solution to the distillation kettle, the ruthenium-containing material reacts with the oxidant to generate ruthenium tetroxide gas, and the ruthenium tetroxide gas flows sequentially through the hot water washing bottle and the cold water washing bottle to remove impurities from the ruthenium tetroxide gas.

[0009] By adopting the above technical solution, the distilled ruthenium tetroxide gas is subjected to gas washing operations by passing through a glass tube in a hot water washing bottle and a cold water washing bottle under the action of gas pressure difference, so as to remove impurities.

[0010] Optionally, the hydrochloric acid absorption bottle includes a hot hydrochloric acid absorption bottle and a first cold hydrochloric acid absorption bottle connected in sequence. The hot hydrochloric acid absorption bottle is connected to the distillation system, and the first cold hydrochloric acid absorption bottle is connected to the vacuum system.

[0011] By adopting the above technical solution, hydrochloric acid in the hot hydrochloric acid absorption bottle and the cold hydrochloric acid absorption bottle absorbs ruthenium tetroxide gas in multiple stages, thereby improving the absorption efficiency and absorption amount of ruthenium tetroxide gas.

[0012] Optionally, the absorption system further includes a test bottle and a vacuum diaphragm valve. The hydrochloric acid absorption bottle also includes a second cold hydrochloric acid absorption bottle. The test bottle is disposed between the first cold hydrochloric acid absorption bottle and the second cold hydrochloric acid absorption bottle. The second cold hydrochloric acid absorption bottle is connected to the vacuum system. The test bottle has a test port, which is sealed by the vacuum diaphragm valve. A cotton swab with a test drug is inserted through the test port to test whether the ruthenium tetroxide gas has been completely absorbed.

[0013] By employing the above technical solution, the presence of ruthenium tetroxide gas is tested in the test bottle to verify whether the ruthenium tetroxide gas is completely absorbed by the hydrochloric acid in the hot hydrochloric acid absorption bottle and the first cold hydrochloric acid absorption bottle. Simultaneously, a second cold hydrochloric acid absorption bottle is installed downstream of the test bottle to recover the ruthenium tetroxide gas, thereby improving safety.

[0014] Optionally, the reduction filtration system includes a reduction vessel, a filter, and a second buffer bottle. The reduction vessel and the second buffer bottle are connected to the vacuum system. The first-stage hydrochloric acid absorption bottle in the hydrochloric acid absorption bottle delivers chlororuthenium acid solution to the reduction vessel and adds a reducing agent to the reduction vessel. The chlororuthenium acid reacts with the reducing agent to generate ruthenium metal. The material in the reduction vessel is pumped to the filter for filtration to obtain ruthenium metal. The reduction vessel is connected to an external washing water supply device to wash the ruthenium metal in the filter. The filtrate is pumped to the second buffer bottle, which is connected to an external wastewater tank.

[0015] By employing the above technical solution, after the hydrochloric acid in the absorption system absorbs the ruthenium tetroxide gas, the solution in the hot hydrochloric acid absorption bottle has a high ruthenium concentration. This solution is then transferred to a reduction vessel. Subsequently, a reducing agent is added to the reduction vessel through the feed port, reducing the ruthenium ions in the solution to ruthenium metal. The material in the reduction vessel is then transferred to a filter under negative pressure for filtration, where the ruthenium metal remains on the filter plates.

[0016] Optionally, the hydrochloric acid absorption bottle is provided with a gas distribution tube, the top of which is connected to the inlet of the hydrochloric acid absorption bottle, the bottom of which extends into the solution inside the hydrochloric acid absorption bottle, and the bottom of the gas distribution tube has several through holes.

[0017] By adopting the above technical solution, the gas is dispersed into multiple microbubbles after passing through these holes, which increases the contact area between the gas and the absorbent liquid, while prolonging the residence time of the bubbles in the absorbent liquid, promoting full mixing and reaction of the gas and liquid phases, and improving the absorption efficiency of ruthenium tetroxide gas.

[0018] A ruthenium refining method, using the aforementioned ruthenium refining apparatus to prepare ruthenium metal, includes the following steps: Raw material preparation: Transfer the ruthenium-containing material to the distillation vessel, calculate the required amount of reagent, first add the reagent from the second reagent bottle to the bottom of the distillation vessel, and then slowly add the reagent from the first reagent bottle to the distillation vessel for distillation; Reaction environment preparation: Heat the distillation vessel, turn on the stirrer of the distillation vessel, and set the temperature inside the distillation vessel to 70-90°C; Absorption of ruthenium tetroxide gas: After the ruthenium tetroxide gas generated by the distillation kettle is washed by hot water washing bottle and cold water washing bottle, the ruthenium tetroxide gas is transported to the absorption system. The hydrochloric acid in the multi-stage hydrochloric acid absorption bottle absorbs the ruthenium tetroxide gas to form chlororuthenium acid solution. To test for ruthenium tetroxide: Open the test port of the test bottle and insert a cotton swab containing acidic thiourea into the test port. Observe whether the color of the cotton swab tip changes. If the cotton swab tip does not change color, it means that the ruthenium tetroxide gas has been completely absorbed. If the cotton swab tip turns blue, it means that there is ruthenium tetroxide gas in the test bottle, but the ruthenium tetroxide gas has not been completely absorbed. The distillation system and absorption system need to be adjusted, and the second cold hydrochloric acid absorption bottle should be used to absorb the ruthenium tetroxide gas. Reduction of ruthenium metal: After the absorption process is complete, the ruthenium concentration in the solution in the hot hydrochloric acid absorption bottle is high. The solution in the hot hydrochloric acid absorption bottle is transferred to the reduction vessel. A reducing agent is added to the reduction vessel, and chlororuthenium acid reacts with the reducing agent to generate ruthenium metal. Filtration of ruthenium metal: The material in the reduction vessel is pumped to a filter for filtration to obtain ruthenium metal; an external washing water supply device washes the ruthenium metal in the filter, and the filtrate is pumped to a second buffer bottle; Transferring the solution in the hydrochloric acid absorption bottle: First transfer the solution in the secondary hydrochloric acid absorption bottle to the first buffer bottle, and then transfer the solution to the previous stage hydrochloric acid absorption bottle; and so on, transferring the solution in the hydrochloric acid absorption bottles in sequence. The third reagent bottle replenishes the final stage hydrochloric acid absorption bottle with new hydrochloric acid solution.

[0019] Optionally, the temperature of the hot water in the hot water washing bottle is 55-65°C.

[0020] By adopting the above technical solution, the high-temperature mixed gas from the distillation vessel first enters the hot water washing bottle, where high-boiling-point impurities condense upon cooling and are dissolved or washed off by the hot water, thus separating from the ruthenium tetroxide gas.

[0021] Optionally, the reagent in the first reagent bottle (12) is a 10% to 50% sodium chlorate solution or a 10% to 20% sodium bromate solution or chlorine gas, and the reagent in the second reagent bottle (13) is a 15% to 36% hydrochloric acid or a 70% to 98% sulfuric acid.

[0022] By adopting the above technical solution, it is beneficial for ruthenium-containing materials to react with oxidants, thereby improving ruthenium recovery efficiency and recovery rate.

[0023] Optionally, the stirring speed of the stirrer in the distillation vessel is 40-50 r / min; the stirring speed of the stirrer in the reduction vessel is 40-50 r / min; and the temperature inside the reduction vessel (32) is 40-80°C.

[0024] By adopting the above technical solution, the stirring speed of the stirrer in the distillation vessel is 40-50 r / min, which is beneficial to improving the reaction between ruthenium-containing materials and oxidants, thereby increasing the ruthenium recovery efficiency and recovery rate. Similarly, the stirring speed of the stirrer in the reduction vessel is 40-50 r / min, which is beneficial to the full reaction between chlororuthenium acid and the reducing agent, further improving the ruthenium metal recovery efficiency and recovery rate.

[0025] In summary, this application includes at least one of the following beneficial technical effects: The hydrochloric acid in the multi-stage hydrochloric acid absorption bottles is used to absorb ruthenium tetroxide gas, generating a chlororuthenium acid solution. In the first-stage absorption bottle, after absorbing ruthenium tetroxide gas, the solution becomes a high-concentration chlororuthenium acid solution, while subsequent absorption bottles contain a low-concentration ruthenium salt solution. After the solution in the first-stage absorption bottle is transferred to the reduction filtration system, the solution in the subsequent absorption bottle is sequentially transferred to the previous absorption bottle, thus achieving a step-by-step concentration replenishment of the hydrochloric acid absorbent within the absorption bottles. Through this multi-stage transfer of solutions, the chlororuthenium acid concentration in the secondary absorption bottles is maintained at a low level, which facilitates the absorption of ruthenium tetroxide gas escaping from the previous absorption bottle. Therefore, this process improves the absorption rate of ruthenium tetroxide gas, fully utilizes the hydrochloric acid absorbent resources, avoids ruthenium waste, and increases the recovery rate of ruthenium metal. The presence of ruthenium tetroxide gas is tested in the test bottle to verify whether the gas is completely absorbed by the hydrochloric acid in the hot hydrochloric acid absorption bottle and the first cold hydrochloric acid absorption bottle. Simultaneously, a second cold hydrochloric acid absorption bottle is installed downstream of the test bottle to recover the ruthenium tetroxide gas, thus improving gas safety. After passing through these pores, the gas is dispersed into multiple tiny bubbles, which increases the contact area between the gas and the absorbent liquid. At the same time, it prolongs the residence time of the bubbles in the absorbent liquid, promotes full mixing and reaction of the gas and liquid phases, and improves the absorption efficiency of ruthenium tetroxide gas. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the ruthenium refining apparatus in Example 1.

[0027] Figure 2 This is a schematic diagram of the distillation system in Example 1.

[0028] Figure 3 This is a schematic diagram of the absorption system in Example 1.

[0029] Figure 4 yes Figure 3 Enlarged view of point A in the middle.

[0030] Figure 5 This is a schematic diagram of the reduction filtration system in Example 1.

[0031] Explanation of reference numerals in the attached drawings: 1. Distillation system; 11. Distillation fume hood; 12. First reagent bottle; 13. Second reagent bottle; 14. Distillation kettle; 15. Hot water washing bottle; 16. Cold water washing bottle; 2. Absorption system; 21. Fixed support frame; 22. Third reagent bottle; 23. Hot hydrochloric acid absorption bottle; 24. First cold hydrochloric acid absorption bottle; 25. Second cold hydrochloric acid absorption bottle; 26. Test bottle; 27. First buffer bottle; 28. Vacuum diaphragm valve; 29. ​​Gas distribution pipe; 291. Through hole; 3. Reduction filtration system; 31. Reduction fume hood; 32. Reduction kettle; 33. Filter; 34. Second buffer bottle; 4. Vacuum system; 5. Washing water supply device; 6. Wastewater tank. Detailed Implementation

[0032] The following is in conjunction with the appendix Figure 1 -5 provides further details regarding this application.

[0033] In this document, the connection between the devices should be understood as "connected via glass tubes". The glass tubes are equipped with multiple valves (electric or pneumatic) to control the transfer of materials. In the accompanying drawings, JY and ZK represent electric valves, and PY represents pneumatic valves; for example, JY01 represents the first electric valve.

[0034] Example 1: This application discloses a ruthenium refining apparatus and method. (Refer to...) Figure 1 The ruthenium refining apparatus and method include a distillation system 1, an absorption system 2, a reduction filtration system 3, and a vacuum system 4.

[0035] Reference Figure 2 The distillation system 1 includes a distillation fume hood 11, a first reagent bottle 12, a second reagent bottle 13, a distillation kettle 14, a hot water washing bottle 15, and a cold water washing bottle 16.

[0036] Reference Figure 2 The distillation vessel 14 is located inside the ruthenium distillation fume hood 11. When ruthenium-containing materials are distilled in the distillation vessel 14, the escaped gas can be extracted in time to avoid accumulation and ensure a safe and clean working environment.

[0037] Reference Figure 2 The first reagent bottle 12 contains an oxidizing agent, and the second reagent bottle 13 contains an acidic solution; the first reagent bottle 12 and the second reagent bottle 13 are connected to the dosing port of the distillation vessel 14. In this embodiment, the reagent in the first reagent bottle 12 is added to the distillation vessel 14 under the control of the first electric valve (JY01); the reagent in the first reagent bottle 12 is added to the distillation vessel 14 under the control of the second electric valve (JY02).

[0038] The reagent in the first reagent bottle 12 is a 10%–50% sodium chlorate solution, a 10%–20% sodium bromate solution, or chlorine gas; the reagent in the second reagent bottle 13 is a 15%–36% hydrochloric acid solution or a 70%–98% sulfuric acid solution. In this embodiment, the first reagent bottle 12 contains a 40% sodium chlorate solution, and the second reagent bottle 13 contains a 36% hydrochloric acid solution.

[0039] After the ruthenium-containing material is added to the distillation vessel 14, 36% hydrochloric acid from the second reagent bottle 13 is added to the distillation vessel 14 as a base to create an acidic environment. Subsequently, the first reagent bottle 12 supplies a 40% sodium chlorate solution (oxidant) to the distillation vessel 14; thus, under acidic conditions, the ruthenium in the ruthenium-containing material reacts with the oxidant to produce ruthenium tetroxide gas.

[0040] Reference Figure 2 The distillation vessel 14 is a jacketed double-walled glass vessel. Heat transfer oil, hot water, or steam supplied by the heating device via pipeline enters the jacket of the distillation vessel 14, contacting the vessel wall for heat transfer and rapidly transferring heat to the material inside. The distillation vessel 14 is equipped with thermocouples to monitor the temperature of the material inside. The temperature control system of the distillation vessel 14 is set with upper and lower limits. When the measured temperature is lower than the preset lower limit, the control system triggers the heating device to start, continuously supplying heat to the vessel. When the measured temperature reaches the preset upper limit, the control system issues a shutdown signal, and the heating device stops operating. This closed-loop control logic achieves precise temperature control of the vessel. In this embodiment, the heating of the distillation vessel 14 is automatically and precisely controlled by a PCL, reducing energy consumption.

[0041] In this embodiment, the temperature inside the distillation vessel is set at 70-90°C. The stirrer in the distillation vessel 14 is turned on, and the stirring speed of the stirrer in the distillation vessel 14 is 40-50 r / min to promote the generation of ruthenium tetroxide gas.

[0042] Reference Figure 2 The distillation vessel 14, hot water washing bottle 15, and cold water washing bottle 16 are connected in series via a glass tube, allowing the ruthenium tetroxide gas generated in the distillation vessel 14 to flow sequentially into the hot water washing bottle 15 and the cold water washing bottle 16. Pure water is supplied to the hot water washing bottle 15 and the cold water washing bottle 16 through a pipeline. The hot water washing bottle 15 is a double-jacketed glass bottle, with external hot water (at a constant temperature of 55-65°C) circulating through the jacket to heat the pure water inside, thereby maintaining the temperature of the pure water inside the hot water washing bottle 15 at 55-65°C.

[0043] Reference Figure 3 The absorption system 2 includes a fixed support frame 21, a third reagent bottle 22, a hydrochloric acid absorption bottle, a test bottle 26, a cold hydrochloric acid absorption bottle, and a first buffer bottle 27.

[0044] Reference Figure 3Along the gas flow direction, several hydrochloric acid absorption bottles are arranged, and these bottles are connected in series via glass tubes, thus forming a multi-stage hydrochloric acid absorption system. The hydrochloric acid absorption system includes a hot hydrochloric acid absorption bottle 23, a first cold hydrochloric acid absorption bottle 24, and a second cold hydrochloric acid absorption bottle 25 connected in series. Along the ruthenium tetroxide flow direction, the hot hydrochloric acid absorption bottle 23 is the first-stage hydrochloric acid absorption bottle, the first cold hydrochloric acid absorption bottle 24 is the second-stage hydrochloric acid absorption bottle, and so on. The final stage of hydrochloric acid absorption bottle is connected to a vacuum system 4 to drive the ruthenium tetroxide gas to flow sequentially through the several hydrochloric acid absorption bottles.

[0045] The hot hydrochloric acid absorption bottle 23 is a double-layered jacketed glass bottle, with external hot water (55-65°C) circulating through the jacket to heat the hydrochloric acid inside the bottle, thus maintaining the temperature of the hydrochloric acid inside the hot hydrochloric acid absorption bottle 23 at 55-65°C. Several first cold hydrochloric acid absorption bottles 24 and second cold hydrochloric acid absorption bottles 25 are provided to absorb ruthenium tetroxide gas in a multi-stage manner.

[0046] Reference Figure 3 In this embodiment, four first cold hydrochloric acid absorption bottles 24 are provided, and the four first cold hydrochloric acid absorption bottles 24 are connected in sequence; two second cold hydrochloric acid absorption bottles 25 are provided, and the two second cold hydrochloric acid absorption bottles 25 are connected in sequence; a test bottle 26 is disposed between the first cold hydrochloric acid absorption bottles 24 and the second cold hydrochloric acid absorption bottles 25. That is, in this embodiment, the hot hydrochloric acid absorption bottle 23, the four first cold hydrochloric acid absorption bottles 24, the test bottle 26, and the two second cold hydrochloric acid absorption bottles 25 are connected in series via a glass tube. The hot hydrochloric acid absorption bottle 23 and the four first cold hydrochloric acid absorption bottles 24 constitute a five-stage hydrochloric acid absorption bottle for ruthenium tetroxide gas. In other embodiments, the number of first cold hydrochloric acid absorption bottles 24 can also be five, six, etc.

[0047] Specifically, hot hydrochloric acid absorption bottle 23 is a first-stage hydrochloric acid absorption bottle, the first cold hydrochloric acid absorption bottle from left to right is a second-stage hydrochloric acid absorption bottle, the second cold hydrochloric acid absorption bottle from left to right is a third-stage hydrochloric acid absorption bottle, the third cold hydrochloric acid absorption bottle from left to right is a fourth-stage hydrochloric acid absorption bottle, and the fourth cold hydrochloric acid absorption bottle from left to right is a fifth-stage hydrochloric acid absorption bottle.

[0048] Reference Figure 3 The third reagent bottle 22 contains hydrochloric acid. Before the device starts operating, the third reagent bottle 22 supplies hydrochloric acid to the hot hydrochloric acid absorption bottle 23, the first cold hydrochloric acid absorption bottle 24, and the second cold hydrochloric acid absorption bottle 25 through the hydrochloric acid delivery pipe. The hydrochloric acid in the hydrochloric acid absorption bottle reacts with ruthenium tetroxide gas to produce chlororuthenium acid solution. The glass tubes connecting the third reagent bottle 22 to several hydrochloric acid absorption bottles are equipped with electric valves, allowing the third reagent bottle 22 to supply hydrochloric acid to a specific hydrochloric acid absorption bottle individually.

[0049] Reference Figure 3 and Figure 4In this embodiment, a gas distribution pipe 29 is provided inside the hydrochloric acid absorption bottle. The top of the gas distribution pipe 29 is connected to the glass tube at the inlet of the hydrochloric acid absorption bottle, and the bottom of the gas distribution pipe 29 extends into the solution inside the hydrochloric acid absorption bottle. Several through holes 291 are opened at the bottom of the gas distribution pipe 29. After passing through these through holes 291, the gas is dispersed into multiple microbubbles, which increases the contact area between the gas and the absorption liquid, prolongs the residence time of the bubbles in the absorption liquid, promotes the full mixing and reaction of the gas and liquid phases, and improves the absorption efficiency of ruthenium tetroxide gas.

[0050] The test bottle 26 is positioned between the first cold hydrochloric acid absorption bottle 24 and the second cold hydrochloric acid absorption bottle 25. The test bottle 26 is used to test whether the ruthenium tetroxide gas has been completely absorbed by the hydrochloric acid in the hot hydrochloric acid absorption bottle 23 and the first cold hydrochloric acid absorption bottle 24. The test port on the test bottle 26 is sealed by a vacuum diaphragm valve 28.

[0051] The inlet of the first buffer bottle 27 is individually connected to the outlet of several hydrochloric acid absorption bottles, and the outlet of the first buffer bottle 27 is individually connected to the inlet of several hydrochloric acid absorption bottles. After the chlororuthenium acid solution in the heated hydrochloric acid absorption bottle 23 (the first-stage hydrochloric acid absorption bottle) is transported to the reduction filtration system 3, the reduction filtration system 3 reduces the chlororuthenium acid in the chlororuthenium acid solution to elemental ruthenium. The solution in the next-stage hydrochloric acid absorption bottle is then transported to the first buffer bottle 27, which in turn transports the solution from the next-stage hydrochloric acid absorption bottle to the previous-stage hydrochloric acid absorption bottle, and so on, transferring the solution from the next-stage hydrochloric acid absorption bottle to the previous-stage hydrochloric acid absorption bottle. Afterwards, the third reagent bottle 22 replenishes hydrochloric acid to the final-stage hydrochloric acid absorption bottle.

[0052] The specific transfer process of the solutions in several hydrochloric acid absorption bottles is as follows: In this embodiment, each of the discharge branches of several hydrochloric acid absorption bottles is equipped with a pneumatic valve. These discharge branches are connected to the main pipe of a three-way connector, and the other two branches of the three-way connector are connected to the reduction filtration system 3 and the first buffer pipe, respectively. Each of the inlet branches of several hydrochloric acid absorption bottles is equipped with an electric valve. These inlet branches are connected to a feed main pipe, one end of which is connected to the third reagent bottle, and the other end of which is connected to the first buffer bottle 27.

[0053] First, during the process of absorbing ruthenium tetroxide gas using hydrochloric acid in the hydrochloric acid absorption bottle, the pneumatic valves (PY05~PY11) on the bottom discharge branch pipes of several hydrochloric acid absorption bottles, the electric valve (JY12) on the glass tube connecting the hydrochloric acid absorption bottle to the reduction filtration system 3, the electric valve (JY13) on the glass tube connecting the discharge port of the hydrochloric acid absorption bottle to the first buffer bottle 27, and the electric valves (JY04~JY10) on the feed branch pipes of several hydrochloric acid absorption bottles are all in the closed state; thus, the ruthenium tetroxide gas can flow through several stages of hydrochloric acid absorption bottles in sequence, and the hydrochloric acid in the several stages of hydrochloric acid absorption bottles can fully absorb the ruthenium tetroxide gas.

[0054] Subsequently, the pneumatic valve (PY05) on the bottom discharge branch of the primary hydrochloric acid absorption bottle (hot hydrochloric acid absorption bottle 23) and the electric valve (JY12) on the glass tube leading from the hydrochloric acid absorption bottle to the reduction filtration system 3 are opened; this allows the chlororuthenium acid solution in the primary hydrochloric acid absorption bottle (hot hydrochloric acid absorption bottle 23) to be transferred to the reduction filtration system 3 through the glass tube. After the chlororuthenium acid solution in the hot hydrochloric acid absorption bottle 23 has been transferred, the hot hydrochloric acid absorption bottle 23 is empty; the pneumatic valve (PY05) on the bottom discharge branch of the hot hydrochloric acid absorption bottle 23 and the electric valve (JY12) on the glass tube leading to the reduction filtration system 3 are closed.

[0055] Next, open the pneumatic valve (PY06) on the bottom discharge branch of the secondary hydrochloric acid absorption bottle (the first cold hydrochloric acid absorption bottle from left to right in the figure) and the electric valve (JY13) on the glass tube leading to the first buffer bottle 27, so that the solution in the secondary hydrochloric acid absorption bottle is transferred to the first buffer bottle 27 through the glass tube. Then, close the pneumatic valve (PY06) on the bottom discharge branch of the secondary hydrochloric acid absorption bottle; at this time, the secondary hydrochloric acid absorption bottle is empty.

[0056] Subsequently, the electric valve (JY11) on the feed main pipe connecting the first buffer bottle 27 to the feed port of the hydrochloric acid absorption bottle, and the electric valve (JY04) on the feed branch pipe of the first hydrochloric acid absorption bottle (hot hydrochloric acid absorption bottle 23) are opened to transfer the solution in the first buffer bottle 27 to the first hydrochloric acid absorption bottle.

[0057] In summary: After the solution in the primary hydrochloric acid absorption bottle (hot hydrochloric acid absorption bottle 23) is transferred to the reduction filtration system 3, through the coordinated action of the hydrochloric acid absorption bottle, the first buffer bottle 27, and the valve on the glass tube, the solution in the secondary hydrochloric acid absorption bottle is first transferred to the first buffer bottle 27, and then the solution in the first buffer bottle 27 is transferred to the primary hydrochloric acid absorption bottle (hot hydrochloric acid absorption bottle 23), thereby achieving the transfer of the solution in the secondary hydrochloric acid absorption bottle to the primary hydrochloric acid absorption bottle.

[0058] Following this process, the solution in the third-stage hydrochloric acid absorption bottle (the second cold hydrochloric acid absorption bottle from the left in the diagram) is transferred sequentially to the second-stage hydrochloric acid absorption bottle (the first cold hydrochloric acid absorption bottle from the left in the diagram); the solution in the fourth-stage hydrochloric acid absorption bottle (the third cold hydrochloric acid absorption bottle from the left in the diagram) is transferred to the third-stage hydrochloric acid absorption bottle (the second cold hydrochloric acid absorption bottle from the left in the diagram); and the solution in the fifth-stage hydrochloric acid absorption bottle (the fourth cold hydrochloric acid absorption bottle from the left in the diagram) is transferred to the fourth-stage hydrochloric acid absorption bottle (the third cold hydrochloric acid absorption bottle from the left in the diagram). Finally, the electric valve (JY03) on the glass tube connecting the third reagent bottle 22 to the hydrochloric acid absorption bottle, and the electric valve (JY10) on the feed branch pipe of the fifth-stage hydrochloric acid absorption bottle are opened; thus achieving the purpose of conveying hydrochloric acid from the third reagent bottle 22 to the fifth-stage hydrochloric acid absorption bottle.

[0059] Reference Figure 5 The reduction filtration system 3 includes a reduction air hood 31, a reduction vessel 32, a filter 33, and a second buffer bottle 34. The reduction vessel 32, the filter 33, and the second buffer bottle 34 are connected in series. The second buffer bottle 34 is connected to the vacuum system 4 so that the reduction filtration system 3 is in a negative pressure environment.

[0060] The reduction vessel 32 is located inside the reduction fume hood 31, allowing escaped gases to be promptly extracted and discharged, preventing accumulation and ensuring a safe and clean working environment. The reduction vessel 32 is connected to the hydrochloric acid absorption bottle and also to the vacuum system 4; thus, the absorbent liquid in the hydrochloric acid absorption bottle is transferred to the reduction vessel 32 through negative pressure.

[0061] After the solution in the hydrochloric acid absorption bottle is transferred to the reduction vessel 32, a reducing agent is added to the reduction vessel 32. The chlororuthenic acid in the solution reacts with the reducing agent to produce ruthenium metal. The material in the reduction vessel 32 is then pumped to the filter 33 for filtration to obtain ruthenium metal.

[0062] The reduction vessel 32 is externally connected to a washing water supply device 5 to wash the ruthenium metal in the filter 33. The filter 33 is connected to a second buffer bottle 34, which is connected to a vacuum system 4, thereby allowing the material in the reduction vessel 32 to be transferred to the filter 33 under negative pressure. The washing water from the washing water supply device 5 repeatedly washes the ruthenium metal on the filter plate in the filter 33, and the filtrate is pumped into the second buffer bottle 34, which is externally connected to a wastewater tank 6. The distillation vessel 14, washing bottle, absorption bottle, test bottle 26, reduction vessel 32, reagent bottle, buffer bottle, and glass tubes used for connection in this device are all made of high-borosilicate glass that is resistant to high temperature and acid and alkali corrosion; thus, the reaction status and material conversion process of the entire ruthenium refining process can be visualized and observed in real time, and the operation of each process can be intuitively grasped.

[0063] The implementation principle of the ruthenium refining apparatus and method in this application is as follows: In a distillation vessel, under acidic and heated conditions, ruthenium in ruthenium-containing materials reacts with an oxidant to produce ruthenium tetroxide gas.

[0064] The distilled ruthenium tetroxide gas, under the action of a pressure difference, passes through a glass tube and successively through a hot water washing bottle 15 and a cold water washing bottle 16 to perform gas washing operations and remove impurities.

[0065] Because other metals in ruthenium-containing materials (such as iron, aluminum, and copper) can form volatile chlorides (such as ferric chloride) in an oxidizing environment. Ruthenium tetroxide gas has a boiling point of 40°C, while the boiling points of these impurity chlorides are typically higher than that of ruthenium tetroxide gas. The hot water in the hot water wash bottle 15 provides an ideal condensation environment for these high-boiling-point impurities. When the high-temperature mixed gas from the distillation vessel 14 first enters the hot water wash bottle 15, the high-boiling-point impurities condense upon cooling and are dissolved or washed off by the hot water, thus separating from the ruthenium tetroxide gas. The hot water in the wash bottle 15 also reduces the risk of ruthenium tetroxide gas decomposition, ensuring stable ruthenium tetroxide gas transmission, reducing the risk of glass pipe blockage, minimizing ruthenium metal loss, and improving ruthenium metal recovery rate.

[0066] After washing in the hot water wash bottle 15, some low-boiling-point impurities and water vapor may still remain in the gas. By placing a cold water wash bottle 16 between the hot water wash bottle 15 and the hot hydrochloric acid absorption bottle 23, the risk of water vapor entering the subsequent hydrochloric acid absorption bottle is reduced, ensuring the stability of the hydrochloric acid concentration and the absorption effect within the absorption bottle. The cold water in the cold water wash bottle 16 condenses and traps the low-to-medium boiling-point impurities that have passed through the hot water bottle, cooling the gas to near room temperature.

[0067] That is, by working together with the hot water washing bottle 15 and the cold water washing bottle 16, impurities in the gas are removed, increasing the proportion of ruthenium tetroxide gas entering the absorption system 2, which is beneficial to improving the recovery rate and efficiency of ruthenium metal.

[0068] The hydrochloric acid in the multi-stage hydrochloric acid absorption bottle is used to absorb ruthenium tetroxide gas, generating a chlororuthenium acid solution. In this embodiment, the temperature of the hot hydrochloric acid absorption bottle 23 is controlled at 55-65°C to reduce the viscosity of the hydrochloric acid, which is beneficial for the diffusion and bubbling of ruthenium tetroxide gas in the liquid, increasing the gas-liquid contact area and enhancing the mass transfer process. Simultaneously, the higher temperature inside the hot hydrochloric acid absorption bottle 23 significantly increases the chemical reaction rate, making the reaction between ruthenium tetroxide gas and hydrochloric acid more rapid and thorough. That is, most of the ruthenium tetroxide gas is absorbed in the hot hydrochloric acid absorption bottle 23 and then converted into chlororuthenium acid. Since the boiling point of ruthenium tetroxide gas is approximately 40°C, controlling the solution temperature in the hot hydrochloric acid absorption bottle 23 at 55-65°C also contributes to the solubility of ruthenium tetroxide gas in the solution, thus improving the absorption efficiency of ruthenium tetroxide.

[0069] The trace amounts of ruthenium tetroxide gas that escaped and were not absorbed in the hot hydrochloric acid absorption bottle 23 will enter the first cold hydrochloric acid absorption bottle 24. According to the law of gas solubility, the lower the temperature, the higher the solubility of the gas in the liquid; cold hydrochloric acid can more effectively dissolve and capture the last remaining ruthenium tetroxide gas. The low temperature environment also helps to condense the trace amounts of ruthenium tetroxide vapor. The presence of the first cold hydrochloric acid absorption bottle 24 ensures that the recovery rate of ruthenium tetroxide gas is close to 100%. This reduces the amount of valuable ruthenium tetroxide gas entering the subsequent vacuum system 4 and being discharged into the atmosphere, thereby improving the recovery rate and efficiency of ruthenium metal.

[0070] The presence of ruthenium tetroxide gas is checked in the test bottle 26 to verify whether the ruthenium tetroxide gas has been completely absorbed by the hydrochloric acid in the hot hydrochloric acid absorption bottle 23 and the first cold hydrochloric acid absorption bottle 24. In other words, this device uses the test bottle 26 to monitor the ruthenium refining process. If the concentration of chlororuthenium acid in the hydrochloric acid absorption bottle is too high, resulting in low ruthenium tetroxide gas absorption efficiency, or if the amount of reagent added is too low, leading to incomplete ruthenium tetroxide gas absorption, the problem can be detected promptly through the test bottle 26, and corresponding solutions can be implemented.

[0071] Meanwhile, a second cold hydrochloric acid absorption bottle 25 is installed downstream of the test bottle 26 to recover ruthenium tetroxide gas and improve safety.

[0072] After the hydrochloric acid in the hot hydrochloric acid absorption bottle 23 (the first-stage hydrochloric acid absorption bottle) absorbs ruthenium tetroxide gas, the solution is converted into a high-concentration chlororuthenium acid solution, and the subsequent hydrochloric acid absorption bottle is a low-concentration ruthenium salt solution.

[0073] After the solution in the first-stage hydrochloric acid absorption bottle (hot hydrochloric acid absorption bottle 23) is transferred to the reduction filtration system 3, the solution in the next-stage hydrochloric acid absorption bottle is transferred to the previous-stage hydrochloric acid absorption bottle in turn, thereby realizing the gradual concentration of hydrochloric acid absorption solution in the hydrochloric acid absorption bottle.

[0074] It is important to note that during normal operation of the equipment, only the high-concentration ruthenium salt solution in the hot hydrochloric acid absorption bottle 23 is transferred to the reduction vessel 32. Specifically, the operator opens the pneumatic valve (PY05) on the bottom discharge branch pipe of the hot hydrochloric acid absorption bottle 23 and the electric valve (JY12) on the glass tube connected to the reduction vessel 32, thereby transferring the solution in the hot hydrochloric acid absorption bottle 23 to the reduction vessel 32. Only when the equipment is to be shut down will the pneumatic valves on the bottom discharge branch pipes of the first cold hydrochloric acid absorption bottle 24 and the second cold hydrochloric acid absorption bottle 25 be opened to transfer all the low-concentration ruthenium salt solution in the cold hydrochloric acid absorption bottles to the reduction vessel 32 for reaction.

[0075] In this embodiment, by progressively concentrating the hydrochloric acid absorbent in the hydrochloric acid absorption bottle, the concentration of chlororuthenium acid in the secondary hydrochloric acid absorption bottle is maintained at a low level. This facilitates the full absorption of ruthenium tetroxide gas escaping from the previous stage hydrochloric acid absorption bottle by the solution in that stage. Thus, through the above operation, the hydrochloric acid absorbent resource is fully utilized, the absorption rate of ruthenium tetroxide gas is improved, ruthenium resource waste is avoided, and the recovery rate of ruthenium metal is increased.

[0076] The device described in this application is an integrated equipment for the entire ruthenium refining process, which realizes continuous operation of the entire process from raw material feeding to the reduction of ruthenium metal. It eliminates the need for additional equipment disassembly or manual transfer of intermediate materials, achieving "one-stop" ruthenium refining production, simplifying the ruthenium refining operation process and improving the efficiency of ruthenium refining.

[0077] Example 2: This Example 2 discloses a ruthenium refining method. This example utilizes a ruthenium-containing material with 40% Ru to recover ruthenium metal. This Example 2 uses the ruthenium refining apparatus from Example 1 to refine ruthenium metal, mainly including the following steps: Preparation: Add pure water to the hot water washing bottle 15 and the cold water washing bottle 16. The hydrochloric acid absorption bottle has a volume of 50L. Add 36% hydrochloric acid from the third reagent bottle 22 to several hydrochloric acid absorption bottles (hot hydrochloric acid absorption bottle 23, first cold hydrochloric acid absorption bottle 24, and second cold hydrochloric acid absorption bottle 25). Turn on the hot water circulation device for the hot water washing bottle 15 and the hot hydrochloric acid absorption bottle 23, maintaining the hot water temperature in the circulation device at 55-65℃, so that the pure water temperature in the hot water washing bottle 15 and the hydrochloric acid temperature in the hot hydrochloric acid absorption bottle 23 are also maintained at 55-65℃. Turn on the vacuum system 4 to maintain a negative pressure state inside the absorption system and the reduction filtration system. In this embodiment, the liquid temperature in the hot water washing bottle 15 and the hot hydrochloric acid absorption bottle 23 is 55℃.

[0078] Raw material preparation: Transfer 5 kg of ruthenium-containing material (containing 40% Ru) into distillation vessel 14, and calculate the required amount of reagent. First, add 36% hydrochloric acid from the second reagent bottle 13 to the distillation vessel 14 as a base, with the opening of the second reagent bottle 13 at 15%~20%. Then, slowly add 40% sodium chlorate solution from the first reagent bottle 12 to the distillation vessel 14, with the opening of the first reagent bottle 12 at 15%~20%. In this embodiment, the opening of the second reagent bottle 13 and the first reagent bottle 12 is 20%. In other embodiments, the opening of the second reagent bottle 13 and the first reagent bottle 12 is any value among 15%, 16%, and 17%.

[0079] Reaction environment preparation: After the reagent addition is completed, the jacket heating device in the distillation vessel 14 is turned on to heat the vessel, setting the temperature inside 14 to 70-90°C. The stirrer in the distillation vessel 14 is then turned on, with a stirring speed of 40-50 r / min, to begin the distillation process. By limiting the temperature inside the distillation vessel and the stirring speed, the reaction between ruthenium and the oxidant in the ruthenium-containing material is improved, thereby increasing the ruthenium recovery efficiency and recovery rate. In this embodiment, the temperature inside the distillation vessel 14 is set at 70°C, and the stirring speed of the stirrer in the distillation vessel 14 is 45 r / min.

[0080] Absorption of ruthenium tetroxide gas: The ruthenium tetroxide gas generated by the distillation vessel 14 is washed by the hot water washing bottle 15 and the cold water washing bottle 16. The ruthenium tetroxide gas is then transported to the absorption system 2. The hydrochloric acid in the multi-stage hydrochloric acid absorption bottle absorbs the ruthenium tetroxide gas to form a chlororuthenium acid solution.

[0081] Testing for ruthenium tetroxide: After 1.5 hours of distillation, observe that no yellow gas is produced in the distillation vessel 14. Open the vacuum diaphragm valve 28. Insert a cotton swab containing acidic thiourea into the test port and observe whether the color of the swab tip changes. If the swab tip does not change color, it indicates that the ruthenium tetroxide gas has been completely absorbed, and the distillation operation is complete. If the swab tip turns blue, it indicates that there is ruthenium tetroxide gas in the test bottle 26, and the ruthenium tetroxide gas absorption is incomplete. It is necessary to adjust the distillation system 1 and the absorption system 2, and use the second cold hydrochloric acid absorption bottle 25 to absorb the ruthenium tetroxide gas.

[0082] Reduction of ruthenium metal: After the distillation and hydrochloric acid absorption operations are completed, the heating device of the distillation vessel 14 is turned off, and the hot water washing bottle 15 and the hot water circulation device of the hot hydrochloric acid absorption bottle 23 are shut off. At this time, the ruthenium concentration in the solution in the hot hydrochloric acid absorption bottle 23 is high. The reduction vessel 32 is kept under negative pressure, and the solution in the hot hydrochloric acid absorption bottle 23 is transferred to the reduction vessel 32.

[0083] A reducing agent is added to the reduction vessel 32. The stirring speed of the stirrer in the reduction vessel 32 is 40-50 r / min, and the reduction temperature inside the reduction vessel 32 is controlled at 40-80°C. In this embodiment, the reduction temperature inside the reduction vessel 32 is controlled at 40°C, and the stirring speed of the stirrer in the reduction vessel 32 is 45 r / min.

[0084] By limiting the temperature inside the reduction vessel 32 and the stirring rate of the stirrer, the reaction between chlororuthenium acid and the reducing agent is facilitated, resulting in the formation of ruthenium metal. In this embodiment, the reducing agent is hydrazine hydrate; chlororuthenium acid reacts with hydrazine hydrate to form ruthenium metal. After 0.5 hours of reduction operation, no reaction occurs when hydrazine hydrate is added to the solution, indicating that the reduction operation is complete.

[0085] Filtering Ruthenium Metal: The material in the reduction vessel 32 is pumped into the filter 33. An external washing water supply device 5 heats water into the filter 33 until it covers the ruthenium metal on the filter plate. The ruthenium metal is manually stirred. After one washing operation, the washing water from the filter 33 is transferred to the second buffer bottle 34 under negative pressure. The same operation is repeated four times. The washing solution is tested with pH paper and found to be neutral. The washing operation is then complete, and ruthenium metal is obtained.

[0086] Drying Ruthenium Metal: Remove the Ruthenium metal from the filter plate and send it to dry and weigh it.

[0087] Transferring the solution in the hydrochloric acid absorption bottle: First transfer the solution in the secondary hydrochloric acid absorption bottle to the first buffer bottle 27, and then transfer the solution to the previous stage hydrochloric acid absorption bottle; and so on, transferring the solution in the hydrochloric acid absorption bottles in sequence. The third reagent bottle 22 replenishes the final stage hydrochloric acid absorption bottle with new hydrochloric acid solution.

[0088] Repeat the above steps to prepare ruthenium metal multiple times.

[0089] Example 3: This Example 3 discloses a ruthenium refining method. The difference between Example 3 and Example 2 is that the liquid temperature in the hot water washing bottle 15 and the hot hydrochloric acid absorption bottle 23 is set to 60°C.

[0090] Example 4: This Example 4 discloses a ruthenium refining method. The difference between Example 4 and Example 2 is that the liquid temperature in the hot water washing bottle 15 and the hot hydrochloric acid absorption bottle 23 is set to 65°C.

[0091] Example 5: This Example 5 discloses a ruthenium refining method. The difference between Example 5 and Example 2 is that the temperature inside the distillation vessel 14 is set to 80°C.

[0092] Example 6: This Example 6 discloses a ruthenium refining method. The difference between Example 6 and Example 2 is that the temperature inside the distillation kettle 14 is set to 90°C.

[0093] Example 7: This Example 7 discloses a ruthenium refining method. The difference between Example 7 and Example 2 is that the stirring speed of the stirrer in the distillation vessel 14 is 40 r / min.

[0094] Example 8: This Example 8 discloses a ruthenium refining method. The difference between Example 8 and Example 2 is that the stirring speed of the stirrer in the distillation vessel 14 is 50 r / min.

[0095] Example 9: This Example 9 discloses a ruthenium refining method. The difference between this Example 9 and Example 2 is that the reduction temperature in the reduction vessel 32 is 60°C.

[0096] Example 10: This Example 10 discloses a ruthenium refining method. The difference between this Example 10 and Example 2 is that the reduction temperature in the reduction vessel 32 is 80°C.

[0097] Example 11: This Example 11 discloses a ruthenium refining method. The difference between Example 11 and Example 2 is that the stirring rate of the stirrer in the reduction vessel 32 is 40 r / min.

[0098] Example 12: This Example 12 discloses a ruthenium refining method. The difference between Example 12 and Example 2 is that the stirring rate of the stirrer in the reduction vessel 32 is 50 r / min.

[0099] Example 13: This Example 13 discloses a ruthenium refining method. The difference between this Example 13 and Example 2 is that in this example, the reagent in the first reagent bottle 12 is a 10% sodium chlorate solution.

[0100] Example 14: This Example 14 discloses a ruthenium refining method. The difference between this Example 14 and Example 2 is that in this example, the reagent in the first reagent bottle 12 is a 50% sodium chlorate solution.

[0101] Example 15: This Example 15 discloses a ruthenium refining method. The difference between this Example 15 and Example 2 is that in this example, the reagent in the first reagent bottle 12 is a 10% sodium bromate solution.

[0102] Example 16: This Example 16 discloses a ruthenium refining method. The difference between Example 16 and Example 2 is that in this example, the reagent in the first reagent bottle 12 is a 15% sodium bromate solution.

[0103] Example 17: This Example 17 discloses a ruthenium refining method. The difference between this Example 17 and Example 2 is that in this example, the reagent in the first reagent bottle 12 is a 20% sodium bromate solution.

[0104] Example 18: This Example 18 discloses a ruthenium refining method. The difference between this Example 18 and Example 2 is that in this example, the reagent in the first reagent bottle 12 is chlorine gas.

[0105] Example 19: This Example 19 discloses a ruthenium refining method. The difference between Example 19 and Example 2 is that in this example, the reagent in the second reagent bottle 13 is 15% hydrochloric acid.

[0106] Example 20: This Example 20 discloses a ruthenium refining method. The difference between this Example 20 and Example 2 is that in this example, the reagent in the second reagent bottle 13 is 25% hydrochloric acid.

[0107] Example 21: This Example 21 discloses a ruthenium refining method. The difference between this Example 21 and Example 2 is that in this example, the reagent in the second reagent bottle 13 is 70% sulfuric acid.

[0108] Example 22: This Example 22 discloses a ruthenium refining method. The difference between this Example 23 and Example 2 is that in this example, the reagent in the second reagent bottle 13 is 80% sulfuric acid.

[0109] Example 23: This Example 23 discloses a ruthenium refining method. The difference between this Example 24 and Example 2 is that in this example, the reagent in the second reagent bottle 13 is 98% sulfuric acid.

[0110] The method described in this application refines ruthenium in ruthenium-containing materials to obtain ruthenium metal with a purity >99.95% and a ruthenium metal recovery rate of approximately 83.7% to 95%, which is higher than the level of existing technology.

[0111] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A ruthenium refining apparatus, characterized in that: The system includes a distillation system (1), an absorption system (2), a reduction filtration system (3), and a vacuum system (4). The distillation system (1), the absorption system (2), and the reduction filtration system (3) are connected in sequence. The vacuum system (4) is connected to the end of the absorption system (2) and the reduction filtration system (3). Ruthenium-containing materials react with an oxidant in the distillation system (1) to generate ruthenium tetroxide gas. The absorption system (2) includes a hydrochloric acid absorption bottle, a third reagent bottle (22), and a first buffer bottle (27). The third reagent bottle (22) is filled with hydrochloric acid and is connected to the hydrochloric acid absorption bottle. There are several hydrochloric acid absorption bottles connected in series to form a multi-stage hydrochloric acid absorption bottle. The first-stage hydrochloric acid absorption bottle is connected to the distillation system (1), and the last-stage hydrochloric acid absorption bottle is connected to the distillation system (1). The absorption bottle is connected to the vacuum system (4). The hydrochloric acid in the hydrochloric acid absorption bottle reacts with ruthenium tetroxide gas to generate chlororuthenium acid solution. The inlet of the first buffer bottle (27) is individually connected to the outlet of several hydrochloric acid absorption bottles. The outlet of the first buffer bottle (27) is individually connected to the inlet of several hydrochloric acid absorption bottles. After the chlororuthenium acid solution in the first-stage hydrochloric acid absorption bottle is transported to the reduction filtration system (3), the solution in the next-stage hydrochloric acid absorption bottle is transported to the first buffer bottle (27). The first buffer bottle (27) transports the solution in the next-stage hydrochloric acid absorption bottle to the previous-stage hydrochloric acid absorption bottle. In this way, the solution in the next-stage hydrochloric acid absorption bottle is transferred to the previous-stage hydrochloric acid absorption bottle. The reduction filtration system (3) reduces the chlororuthenium acid in the chlororuthenium acid solution to ruthenium metal.

2. The ruthenium refining apparatus according to claim 1, characterized in that: The distillation system (1) includes a ruthenium distillation fuze (11), a first reagent bottle (12), a second reagent bottle (13), a distillation vessel (14), a hot water washing bottle (15), and a cold water washing bottle (16). The first reagent bottle (12) contains an oxidant, the second reagent bottle (13) contains an acidic solution, the distillation vessel (14) is located inside the ruthenium distillation fuze (11), the ruthenium-containing material is placed in the distillation vessel (14), the first reagent bottle (12) delivers the oxidant to the distillation vessel (14), the second reagent bottle (13) delivers the acidic solution to the distillation vessel (14), the ruthenium-containing material reacts with the oxidant to generate ruthenium tetroxide gas, and the ruthenium tetroxide gas flows sequentially through the hot water washing bottle (15) and the cold water washing bottle (16) to remove impurities from the ruthenium tetroxide gas.

3. The ruthenium refining apparatus according to claim 1, characterized in that: The hydrochloric acid absorption bottle includes a hot hydrochloric acid absorption bottle (23) and a first cold hydrochloric acid absorption bottle (24) connected in sequence. The hot hydrochloric acid absorption bottle (23) is connected to the distillation system (1), and the first cold hydrochloric acid absorption bottle (24) is connected to the vacuum system (4).

4. The ruthenium refining apparatus according to claim 3, characterized in that: The absorption system (2) also includes a test bottle (26) and a vacuum diaphragm valve (28). The hydrochloric acid absorption bottle also includes a second cold hydrochloric acid absorption bottle (25). The test bottle (26) is located between the first cold hydrochloric acid absorption bottle (24) and the second cold hydrochloric acid absorption bottle (25). The second cold hydrochloric acid absorption bottle (25) is connected to the vacuum system (4). The test bottle (26) is provided with a test port, which is sealed by the vacuum diaphragm valve (28). A cotton swab with a test drug is inserted through the test port to test whether the ruthenium tetroxide gas has been completely absorbed.

5. The ruthenium refining apparatus according to claim 1, characterized in that: The reduction filtration system (3) includes a reduction vessel (32), a filter (33), and a second buffer bottle (34). The reduction vessel (32) and the second buffer bottle (34) are connected to the vacuum system (4). The first-stage hydrochloric acid absorption bottle in the hydrochloric acid absorption bottle delivers chlororuthenic acid solution to the reduction vessel (32) and adds a reducing agent to the reduction vessel (32). The chlororuthenic acid reacts with the reducing agent to generate ruthenium metal. The material in the reduction vessel (32) is pumped to the filter (33) for filtration to obtain ruthenium metal. The reduction vessel (32) is connected to a washing water supply device (5) to wash the ruthenium metal in the filter (33). The filtrate is pumped to the second buffer bottle (34), and the second buffer bottle (34) is connected to a wastewater tank (6).

6. The ruthenium refining apparatus according to claim 1, characterized in that: The hydrochloric acid absorption bottle is provided with a gas distribution tube (29). The top of the gas distribution tube (29) is connected to the glass tube of the feed port of the hydrochloric acid absorption bottle. The bottom of the gas distribution tube (29) extends into the solution inside the hydrochloric acid absorption bottle. Several through holes (291) are opened at the bottom of the gas distribution tube (29).

7. A method for refining ruthenium, characterized in that: The preparation of ruthenium metal using any of the ruthenium refining apparatuses of claims 1 to 6 comprises the following steps: Raw material preparation: Transfer the ruthenium-containing material to the distillation vessel (14), calculate the required amount of reagent, first add the acidic solution in the second reagent bottle (13) to the distillation vessel (14) as a base, and then slowly add the oxidant in the first reagent bottle (12) to the distillation vessel (14) for distillation; Reaction environment preparation: Heat the distillation vessel (14), turn on the stirrer of the distillation vessel (14), and set the temperature inside the distillation vessel (14) to 70-90°C; Absorption of ruthenium tetroxide gas: After the ruthenium tetroxide gas generated by the distillation vessel (14) is washed by the hot water washing bottle (15) and the cold water washing bottle (16), the ruthenium tetroxide gas is transported to the absorption system (2). The hydrochloric acid in the multi-stage hydrochloric acid absorption bottle absorbs the ruthenium tetroxide gas to form a chlororuthenium acid solution. Test for ruthenium tetroxide: Open the test port of the test bottle (26), insert a cotton swab with acidic thiourea into the test port, and observe whether the color of the cotton swab tip changes; if the cotton swab tip does not change color, it means that the ruthenium tetroxide gas has been completely absorbed; if the cotton swab tip turns blue, it means that there is ruthenium tetroxide gas in the test bottle (26), and the ruthenium tetroxide gas is not completely absorbed. It is necessary to adjust the distillation system (1) and the absorption system (2), and use the second cold hydrochloric acid absorption bottle (25) to absorb the ruthenium tetroxide gas. Reduced ruthenium metal: After the absorption process is complete, the ruthenium concentration in the solution in the hot hydrochloric acid absorption bottle (23) is high. The solution in the hot hydrochloric acid absorption bottle (23) is transferred to the reduction vessel (32). A reducing agent is added to the reduction vessel (32), and chlororuthenium acid reacts with the reducing agent to generate ruthenium metal. Filtering ruthenium metal: The material in the reduction vessel (32) is pumped to the filter (33) for filtration to obtain ruthenium metal; the external washing water supply device (5) washes the ruthenium metal in the filter (33), and the filtrate is pumped to the second buffer bottle (34); Transferring the solution in the hydrochloric acid absorption bottle: First transfer the solution in the next stage hydrochloric acid absorption bottle to the first buffer bottle (27), and then transfer the solution to the previous stage hydrochloric acid absorption bottle; and so on, transferring the solution in the hydrochloric acid absorption bottle in turn, and the third reagent bottle (22) replenishes the final stage hydrochloric acid absorption bottle with new hydrochloric acid solution.

8. The ruthenium refining method according to claim 7, characterized in that: The temperature of the hot water in the hot water washing bottle (15) is 55-65°C.

9. The ruthenium refining method according to claim 7, characterized in that: The reagent in the first reagent bottle (12) is a 10% to 50% sodium chlorate solution or a 10% to 20% sodium bromate solution or chlorine gas, and the reagent in the second reagent bottle (13) is a 15% to 36% hydrochloric acid or a 70% to 98% sulfuric acid.

10. The ruthenium refining method according to claim 7, characterized in that: The stirring speed of the stirrer in the distillation vessel (14) is 40-50 r / min; the stirring speed of the stirrer in the reduction vessel (32) is 40-50 r / min; and the reduction temperature in the reduction vessel (32) is 40-80°C.

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