CN111054933A - Method for preparing high-purity rhodium powder from platinum-rhodium waste - Google Patents
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Abstract
The invention relates to a method for preparing high-purity rhodium powder from platinum-rhodium waste, which can separate platinum from rhodium basically by adopting multiple hydrolysis precipitation, can remove a very small amount of platinum by adopting strong ammonia water precipitation, can remove base metal ions by adopting ion exchange, can remove trace platinum by extraction, and the content of the prepared pure rhodium is more than or equal to 99.99 percent. The method disclosed by the invention is simple to operate, environment-friendly, high in safety, high in economy and reliable in product quality.
Description
Technical Field
The invention belongs to the field of precious metal resource recovery and purification, and particularly relates to a method for preparing high-purity rhodium powder from platinum-rhodium waste.
Background
Typical noble metal elements include gold, silver, platinum, palladiumRhodium, iridium, ruthenium, osmium, and the like, and the contents thereof in the earth crust are rare. Especially platinum group metal elements, are very scarcely occupied in the earth's crust, and each ton of the solid matter of the earth's crust contains from a few tenths of grams to a few tenths of grams, of which rhodium or the like is the least, and one ton of the solid matter of the earth's crust contains about 1X 10-3One ton of crust solid matter contains about 5X 10 grams of rhodium-3And (3) gram of platinum.
Platinum and rhodium have the characteristics of high melting point, good electrical conductivity, corrosion resistance and high-temperature stability, and simultaneously have high-temperature strength and strong high-temperature creep capability, so that the platinum and the rhodium become important materials for modern industry and national defense construction, are widely applied to aviation, aerospace, missiles, rockets, atomic energy, micro-electro technology, chemical industry, glass industry, gas purification and metallurgical industry, and have increasingly enhanced functions in high and new technology industry, so the platinum and the rhodium are known as vitamins and modern new metals in modern industry.
Under the condition of resource shortage, the full utilization of domestic platinum group metal mineral resources and secondary resource recovery become more and more important. The preparation method of the platinum and rhodium can be obtained by layer-by-layer refining from platinum group metal mineral resources, and can also be used for recovering platinum and rhodium products which are invalid in the purification application. Because mineral resources are very rare, the platinum-rhodium products which are out of work in the recovery and purification application are mainly adopted at present.
The platinum-rhodium alloy product polluted by impurities, namely the failed platinum-rhodium alloy product, can be used as a raw material of high-purity rhodium to obtain platinum powder and rhodium powder with certain purity, and then the platinum-rhodium alloy product is put into production again. The existing process is to remove impurities from platinum and rhodium by a physical process technology of smelting (charging oxidizing gas), and then to separate platinum powder and rhodium powder by a chemical method, wherein the purity of rhodium can only reach about 99.9%, the method is difficult to reach the purity of rhodium of 99.99%, and has the defects of large energy consumption, complex process, large environmental pollution and quite high economic cost due to the adoption of a strong oxidant in the chemical separation process. As a key material of a nuclear power emitter and industrial electrode materials in the fields of aviation industry, metallurgy and petrochemical industry and the like, high-purity rhodium is required, and the material purity is a key factor influencing the comprehensive performance. Therefore, how to economically and efficiently separate and extract high-purity rhodium powder with the purity of 99.99 percent from platinum rhodium waste is a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity rhodium powder from platinum-rhodium waste, which can separate platinum from rhodium basically by adopting multiple hydrolysis precipitation, can remove a small amount of platinum by adopting strong ammonia water precipitation, can remove base metal ions by adopting ion exchange, can remove trace platinum by extraction, and can prepare the high-purity rhodium with the content of 99.99 percent. The method has the advantages of simple operation, environmental protection, high safety and reliable product quality.
The method for preparing high-purity rhodium powder from platinum-rhodium waste comprises the following steps:
1) primary rhodium hydroxide precipitation:
taking platinum-containing rhodium waste, heating and dissolving the platinum-containing rhodium waste by aqua regia, concentrating, adding 37% concentrated hydrochloric acid to remove nitrate until no yellow smoke is emitted, adding sodium chloride solid, evaporating to dryness, heating water to dissolve to obtain a platinum-rhodium solution, boiling, adjusting the pH value of the platinum-rhodium solution to 9-11 by using chlor-alkali, separating out a rhodium hydroxide precipitate, standing, filtering, washing the precipitate by using a sodium chloride solution, mixing filtrate with cleaning solution, and waiting for platinum purification;
2) and (3) secondary rhodium hydroxide precipitation:
dissolving the rhodium hydroxide precipitate obtained in the step 1) with concentrated hydrochloric acid, concentrating, adding water for dissolution, boiling, adjusting the pH value to 9-11 with chlor-alkali, precipitating the rhodium hydroxide precipitate, standing, filtering, washing the precipitate with a sodium chloride solution, combining the filtrate with a cleaning solution, and waiting for platinum purification;
3) primary ion exchange:
dissolving the rhodium hydroxide precipitate obtained in the step 2) with concentrated hydrochloric acid, concentrating, adding water for dissolution, adjusting the pH value to 1.5-2 with sodium hydroxide, standing, filtering, and exchanging the filtrate with cation resin;
4) and (3) performing tertiary rhodium hydroxide precipitation:
boiling the exchange solution, adjusting the pH value to 9-11 with chlor-alkali, precipitating rhodium hydroxide precipitate, standing, filtering, washing the precipitate with a sodium chloride solution, and combining the filtrate and a cleaning solution to obtain platinum to be purified;
5) secondary ion exchange:
dissolving the rhodium hydroxide precipitate obtained in the step 4) by using concentrated hydrochloric acid, concentrating to be nearly dry, adding water to dissolve until the concentration is 20-40 g/L, adjusting the pH value to be 1.5-2 by using concentrated ammonia water, standing, filtering, and exchanging the filtrate by using cation resin to obtain an exchange solution 1;
6) primary extraction:
concentrating the exchange solution 1 obtained in the step 5) to be nearly dry, dissolving the exchange solution in a hydrochloric acid solution, pouring tributyl phosphate balanced by 4 mol of hydrochloric acid, adding 5-15 g/L of sodium chlorate, stirring for 10-20 minutes, standing for layering, and discharging the lower rhodium solution 1;
7) secondary extraction:
pouring tributyl phosphate balanced by hydrochloric acid into the rhodium solution 1 obtained in the step 6), adding 5-15 g/L of sodium chlorate, stirring for 10-20 minutes, standing for layering, and discharging the lower rhodium solution 2;
8) and (3) three times of ion exchange:
concentrating the rhodium solution 2 obtained in the step 7) to be nearly dry, adding water for dissolving, adjusting the pH value to be 1.5-2 by using sodium hydroxide, filtering, and performing cation resin exchange on the filtrate to obtain an exchange solution 2;
9) reduction:
continuously stirring, adding a sodium hydroxide solution into the exchange solution 2 obtained in the step 8), adjusting the pH value to 8-10, heating to boil, adding an 80% hydrazine hydrate solution, maintaining the temperature of 60-80 ℃ until the solution is clear and transparent, and completely reducing rhodium to obtain rhodium precipitate;
10) and (3) calcining:
filtering the rhodium precipitate obtained in the step 9), cleaning the rhodium precipitate with hot water to be neutral, putting the rhodium precipitate into a crucible, and calcining the rhodium precipitate for 20-40 minutes at 450-650 ℃ to obtain rhodium powder;
11) introducing hydrogen:
and (3) putting the rhodium powder obtained in the step 10) into a porcelain boat, putting the porcelain boat in a tube furnace, introducing hydrogen, keeping the temperature for 1-2 hours, continuously introducing the hydrogen, cooling the furnace to 300 ℃, and closing the hydrogen to obtain the high-purity rhodium powder with the purity of 99.99%.
The dosage of the sodium chloride solid in the step 1) is 0.5-0.7 time of the weight of the platinum rhodium waste.
The platinum-rhodium waste of step 1) is a failed platinum-rhodium alloy product with rhodium content less than 20%.
The concentration of the chlor-alkali in the step 1) and the step 2) is 5-20%.
And 3), 4) and 8) the sodium chloride solution is 5-15%.
The standing time of the steps 1), 2) and 4) is more than or equal to 5 hours.
Step 3) and step 5) are carried out, wherein the rest time is 24 hours.
The concentration in the steps 1), 2) and 3) is only required to be that a crystal film appears on the liquid surface.
The washing precipitation of the steps 1), 2) and 4) is washing 3 times.
Step 9) volume of hydrazine hydrate solution and rhodium: weight 1ml hydrazine hydrate: 1 g of rhodium.
The method adopts repeated hydrolysis precipitation to separate most of the platinum and rhodium, the concentrated ammonia water precipitation can remove a small amount of platinum, the ion exchange is used for removing base metal ions, and the extraction is used for removing trace platinum.
The beneficial effects of the invention mainly comprise the following three aspects:
1. before secondary ion exchange, the PH value of rhodium solution is adjusted by concentrated ammonia water, a small amount of platinum is removed, and the burden of platinum extraction is reduced;
2. in the past, chlorine gas is introduced into extract liquor, the chlorine gas is prepared by the reaction of concentrated hydrochloric acid and potassium permanganate, and the process has strong oxidant potassium permanganate, pollution of concentrated hydrochloric acid and chlorine gas, waste liquid discharge pollution, waste gas and waste liquid treatment and dangerous operation. The invention adopts the reaction of adding sodium chlorate solid, sodium chlorate and hydrochloric acid in the extraction liquid, and has the advantages of simple and convenient operation, safety and environmental protection because a strong oxidant potassium permanganate is not used;
3. compared with the traditional method, the method has the advantages of short process operation, high efficiency and capability of obtaining high-purity rhodium powder with the content of 99.99 percent.
Detailed Description
Example 1
1. Primary rhodium hydroxide precipitation:
heating and dissolving a failed platinum-rhodium alloy product containing 5% of rhodium, heating and dissolving aqua regia, concentrating to a small volume (only when a crystal film appears on the liquid surface), adding 37% concentrated hydrochloric acid to remove nitrate until no yellow smoke emerges, adding sodium chloride solid which is 0.5 times of the weight of the failed platinum-rhodium alloy product, evaporating to dryness, heating water to dissolve to obtain a platinum-rhodium solution, boiling, adjusting the pH to 9 by using 5% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hours, filtering, washing and precipitating for 3 times by using a 5% sodium chloride solution, combining filtrate and cleaning solution, and waiting for purifying platinum;
2. and (3) secondary rhodium hydroxide precipitation:
dissolving rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to small volume (only when crystal membrane appears on the liquid surface), adding water for dissolving, boiling, adjusting pH to 9 with 5% chlor-alkali, precipitating rhodium hydroxide precipitate, standing for about 5 hours, filtering, washing precipitate with 5% sodium chloride solution for 3 times, mixing filtrate and cleaning solution, and treating platinum to be purified;
3. primary ion exchange:
dissolving rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating until crystal film appears on the liquid surface, and dissolving with water. Adjusting pH to 1.5-2 with 5% sodium hydroxide, standing for 24 hr, filtering, and passing the filtrate through clean 732 cation exchange resin;
4. and (3) performing tertiary rhodium hydroxide precipitation:
boiling the exchange solution, adjusting the pH of the solution to 9 by using 5% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hours, filtering, washing the precipitate for 3 times by using a 5% sodium chloride solution, and combining the filtrate and a cleaning solution to obtain platinum to be purified;
5. secondary ion exchange:
dissolving the rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to near dryness, adding water to dissolve until the concentration is 20-40 g/L, adjusting the pH value of the solution to 1.5-2 with concentrated ammonia water, standing for 24 hours, filtering, and exchanging the filtrate with clean 732 cation resin;
6. primary extraction:
concentrating the exchange solution to be nearly dry, adding water for dissolving, dissolving by using 4 mol of hydrochloric acid solution, pouring tributyl phosphate balanced by using 4 mol of hydrochloric acid, adding 5 g/L of analytically pure sodium chloride, stirring for 10-12 minutes, standing for layering, and discharging lower-layer rhodium solution.
7. Secondary extraction:
pouring the rhodium solution obtained in the step 6 into tributyl phosphate balanced by 4 mol of hydrochloric acid, adding 5 g/L of analytically pure sodium chloride, stirring for 10-12 minutes, standing for layering, and discharging the lower-layer rhodium solution;
8. and (3) three times of ion exchange:
concentrating the rhodium solution obtained in the step 7 to be nearly dry, adding water to dissolve the rhodium solution, adjusting the pH value to be 1.5-2 by using 5% sodium hydroxide, filtering, and exchanging the filtrate by using clean 732 cation resin;
9. reduction, calcination and hydrogen introduction:
adding 10% sodium hydroxide solution into the exchange solution under continuous stirring, adjusting the pH value of the solution to 8-10, heating to boil, adding 80% hydrazine hydrate (1 g of rhodium and 1ml of hydrazine hydrate), maintaining the temperature at 60-65 ℃ until the solution is clear and transparent, and completely precipitating the rhodium after reduction.
10. The rhodium precipitate is filtered, washed to be neutral by hot water, and the precipitate is calcined in a crucible for 40 minutes at 450 ℃. And (3) putting the calcined powder into a porcelain boat, putting the porcelain boat into a tubular furnace, introducing hydrogen into the furnace at 650 ℃, keeping the temperature for 2 hours, continuously introducing the hydrogen, cooling the furnace to 300 ℃, and closing the hydrogen to obtain the high-purity rhodium.
Example 2
1. Primary rhodium hydroxide precipitation:
heating and dissolving a failed platinum-rhodium alloy product containing 10% of rhodium by aqua regia, concentrating to a small volume (a crystal film appears on the liquid surface), adding 37% concentrated hydrochloric acid to remove nitrate until no yellow smoke emerges, adding sodium chloride solid which is 0.5-0.7 times of the weight of the failed platinum-rhodium alloy product, evaporating to dryness, dissolving by hot water to obtain a platinum-rhodium solution, boiling, adjusting the pH of the solution to 10 by 10% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hours, filtering, washing and precipitating for 3 times by using a 10% sodium chloride solution, combining filtrate with a cleaning solution, and waiting for purifying platinum;
2. and (3) secondary rhodium hydroxide precipitation:
dissolving rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to small volume (crystal film appears on liquid surface), adding water for dissolving, boiling, adjusting pH to 10 with 10% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hr, filtering, cleaning precipitate with 10% sodium chloride solution for 3 times, mixing filtrate and cleaning solution, and treating platinum;
3. primary ion exchange:
dissolving rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to small volume (crystal film appears on liquid surface), and dissolving with water. Adjusting pH of the solution to 1.5-2 with 10% sodium hydroxide, standing for 24 hr, filtering, and passing the filtrate through clean 732 cation exchange resin;
4. and (3) performing tertiary rhodium hydroxide precipitation:
boiling the exchange solution, adjusting the pH value of the solution to 10 by using 10% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hours, filtering, cleaning the precipitate for 3 times by using 10% sodium chloride solution, combining the filtrate and the cleaning solution, and waiting for platinum purification;
5. secondary ion exchange:
dissolving the rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to near dryness, adding water to dissolve until the concentration is 20-40 g/L, adjusting the pH value of the solution to 1.5-2 with concentrated ammonia water, standing for 24 hours, filtering, and exchanging the filtrate with clean 732 cation resin.
6. Primary extraction:
concentrating the exchange solution to be nearly dry, dissolving the exchange solution by using 4 mol of hydrochloric acid solution, pouring tributyl phosphate balanced by using 4 mol of hydrochloric acid, adding 10 g/L of analytically pure sodium chloride, stirring for 10-12 minutes, standing for layering, and discharging lower-layer rhodium solution;
7. secondary extraction:
and (3) pouring the rhodium solution obtained in the step (6) into tributyl phosphate balanced by 4 mol of hydrochloric acid, adding 10 g/L of analytically pure sodium chloride, stirring for 10-12 minutes, standing for layering, and discharging the lower-layer rhodium solution.
8. And (3) three times of ion exchange:
concentrating the rhodium solution obtained in the step 7 to be nearly dry, adding water for dissolving, adjusting the pH value of the solution to be 1.5-2 by using 10% sodium hydroxide, filtering, and exchanging the filtrate by using clean 732 cation resin;
9. reduction, calcination and hydrogen introduction:
adding 10-20% sodium hydroxide solution into the exchange solution under continuous stirring to adjust the pH value of the solution to 8-10, heating to boil, adding 80% hydrazine hydrate (1 g rhodium plus 1ml hydrazine hydrate), maintaining the temperature at 70 +/-2 ℃ until the solution is clear and transparent, and completely precipitating the rhodium after reduction.
The rhodium precipitate is filtered, washed by hot water, put into a crucible, calcined at 580 ℃ for 25 minutes. And (3) putting the calcined powder into a porcelain boat, putting the porcelain boat into a tubular furnace, introducing hydrogen into the furnace at 700 ℃, keeping the temperature for 1.5 hours, continuously introducing the hydrogen, cooling the furnace to 300 ℃, and closing the hydrogen to obtain the high-purity rhodium.
Example 3
1. Primary rhodium hydroxide precipitation:
heating and dissolving a failed platinum-rhodium alloy product containing 20% of rhodium, heating and dissolving aqua regia, concentrating to a small volume (a crystal film appears on the liquid surface), adding 37% concentrated hydrochloric acid to remove nitrate until no yellow smoke emerges, adding sodium chloride solid with the weight 0.5-0.7 times that of platinum and rhodium, evaporating to dryness, heating water for dissolving to obtain a platinum-rhodium solution, boiling, adjusting the pH value of the solution to 11 by using 20% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hours, filtering, cleaning and precipitating for 3 times by using 15% sodium chloride solution, combining filtrate with cleaning fluid, and waiting for purifying platinum;
2. and (3) secondary rhodium hydroxide precipitation:
dissolving rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to small volume (crystal film appears on liquid surface), adding water for dissolving, boiling, adjusting pH to 11 with 20% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hr, filtering, washing precipitate with 15% sodium chloride solution for 3 times, mixing filtrate and cleaning solution, and purifying platinum;
3. primary ion exchange:
dissolving rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to small volume (crystal film appears on liquid surface), and dissolving with water. Adjusting pH to 1.5-2 with 15% sodium hydroxide, standing for 24 hr, filtering, and passing the filtrate through clean 732 cation exchange resin;
4. and (3) performing tertiary rhodium hydroxide precipitation:
boiling the exchange solution, adjusting the pH value to 11 with 20% chlor-alkali, precipitating rhodium hydroxide, standing for about 5 hours, filtering, cleaning the precipitate with 15% sodium chloride solution, combining the filtrate and the cleaning solution, and waiting for platinum purification;
5. secondary ion exchange:
dissolving the rhodium hydroxide precipitate with concentrated hydrochloric acid, concentrating to near dryness, dissolving with water, adjusting pH to 1.5-2 with concentrated ammonia water, standing for 24 hr, filtering, and passing the filtrate through clean 732 cation resin exchange;
6. primary extraction:
concentrating the exchange solution to be nearly dry, dissolving the exchange solution by using 4 mol of hydrochloric acid solution, pouring tributyl phosphate balanced by using 4 mol of hydrochloric acid, adding 15 g/L of analytically pure sodium chloride, stirring for 10-12 minutes, standing for layering, and discharging lower-layer rhodium solution;
7. secondary extraction:
pouring the rhodium solution obtained in the step 6 into tributyl phosphate balanced by 4 mol of hydrochloric acid, adding 15 g/L of analytically pure sodium chloride, stirring for 10-12 minutes, standing for layering, and discharging the lower-layer rhodium solution;
8. and (3) three times of ion exchange:
concentrating the rhodium solution obtained in the step 7 to be nearly dry, adding water for dissolving, adjusting the pH value of the solution to be 1.5-2 by using 20% sodium hydroxide, filtering, and exchanging the filtrate by using clean 732 cation resin;
9. reduction, calcination and hydrogen introduction:
adding 20% sodium hydroxide solution into the exchange liquid under continuous stirring, adjusting the pH value to 10, heating to boil, adding 80% hydrazine hydrate (1 g of rhodium and 1ml of hydrazine hydrate), maintaining the temperature at 76-80 ℃ until the solution is clear and transparent, and completely precipitating the rhodium after reduction.
The rhodium precipitate is filtered, washed by hot water, put into a crucible, calcined at 650 ℃ for 20 minutes. And (3) putting the calcined powder into a porcelain boat, putting the porcelain boat into a tubular furnace, introducing hydrogen into the furnace at 800 ℃, keeping the temperature for 1 hour, continuously introducing the hydrogen, cooling the furnace to 300 ℃, and closing the hydrogen to obtain the high-purity rhodium.
The high-purity rhodium obtained in examples 1 to 3 was taken, and the contents of the respective components were measured, and the results are shown in the following table:
| example 1 | Example 2 | Example 3 | ||
| Impurity element | Content (%) | Content (%) | Content (%) | |
| Platinum (II) | Pt | 0.0007 | 0.0005 | 0.0007 |
| Ruthenium (II) | Ru | 0.0005 | 0.0005 | 0.0005 |
| Iridium (III) | Ir | 0.0005 | 0.0005 | 0.0005 |
| Palladium (II) | Pd | 0.0005 | 0.0005 | 0.0005 |
| Gold (Au) | Au | 0.0005 | 0.0005 | 0.0005 |
| Silver (Ag) | Ag | 0.0005 | 0.0005 | 0.0005 |
| Copper (Cu) | Cu | 0.0005 | 0.0005 | 0.0005 |
| Iron | Fe | 0.0005 | 0.0005 | 0.0005 |
| Nickel (II) | Ni | 0.0005 | 0.0005 | 0.0005 |
| Aluminium | Al | 0.0004 | 0.0005 | 0.0005 |
| Lead (II) | Pb | 0.0005 | 0.0002 | 0.0005 |
| Manganese oxide | Mn | 0.0005 | 0.0005 | 0.0005 |
| Magnesium alloy | Mg | 0.0001 | 0.0001 | 0.0001 |
| Tin (Sn) | Sn | 0.0005 | 0.0005 | 0.0005 |
| Silicon | Si | 0.0005 | 0.0005 | 0.0005 |
| Zinc | Zn | 0.0005 | 0.0005 | 0.0005 |
| Cadmium (Cd) | Cd | 0.0005 | 0.0005 | 0.0005 |
| Cobalt | Co | 0.0005 | 0.0005 | 0.0005 |
| Total amount of impurities | 0.0087 | 0.0083 | 0.0088 | |
| Rhodium | Rh | ＞99.99 | ＞99.99 | ＞99.99 |
Claims (10)
1. A method for preparing high-purity rhodium powder from platinum-rhodium waste is characterized by comprising the following steps:
1) primary rhodium hydroxide precipitation:
taking platinum-containing rhodium waste, heating and dissolving the platinum-containing rhodium waste by aqua regia, concentrating, adding 37% concentrated hydrochloric acid to remove nitrate until no yellow smoke is emitted, adding sodium chloride solid, evaporating to dryness, heating water to dissolve to obtain a platinum-rhodium solution, boiling, adjusting the pH value of the platinum-rhodium solution to 9-11 by using chlor-alkali, separating out a rhodium hydroxide precipitate, standing, filtering, washing the precipitate by using a sodium chloride solution, mixing filtrate with cleaning solution, and waiting for platinum purification;
2) and (3) secondary rhodium hydroxide precipitation:
dissolving the rhodium hydroxide precipitate obtained in the step 1) with concentrated hydrochloric acid, concentrating, adding water for dissolution, boiling, adjusting the pH value to 9-11 with chlor-alkali, precipitating the rhodium hydroxide precipitate, standing, filtering, washing the precipitate with a sodium chloride solution, combining the filtrate with a cleaning solution, and waiting for platinum purification;
3) primary ion exchange:
dissolving the rhodium hydroxide precipitate obtained in the step 2) with concentrated hydrochloric acid, concentrating, adding water for dissolution, adjusting the pH value to 1.5-2 with sodium hydroxide, standing, filtering, and exchanging the filtrate with cation resin;
4) and (3) performing tertiary rhodium hydroxide precipitation:
boiling the exchange solution, adjusting the pH value to 9-11 with chlor-alkali, precipitating rhodium hydroxide precipitate, standing, filtering, washing the precipitate with a sodium chloride solution, and combining the filtrate and a cleaning solution to obtain platinum to be purified;
5) secondary ion exchange:
dissolving the rhodium hydroxide precipitate obtained in the step 4) by using concentrated hydrochloric acid, concentrating to be nearly dry, adding water to dissolve until the concentration is 20-40 g/L, adjusting the pH value to be 1.5-2 by using concentrated ammonia water, standing, filtering, and exchanging the filtrate by using cation resin to obtain an exchange solution 1;
6) primary extraction:
concentrating the exchange solution 1 obtained in the step 5) to be nearly dry, dissolving the exchange solution in a hydrochloric acid solution, pouring tributyl phosphate balanced by 4 mol of hydrochloric acid, adding 5-15 g/L of sodium chlorate, stirring for 10-20 minutes, standing for layering, and discharging the lower rhodium solution 1;
7) secondary extraction:
pouring tributyl phosphate balanced by hydrochloric acid into the rhodium solution 1 obtained in the step 6), adding 5-15 g/L of sodium chlorate, stirring for 10-20 minutes, standing for layering, and discharging the lower rhodium solution 2;
8) and (3) three times of ion exchange:
concentrating the rhodium solution 2 obtained in the step 7) to be nearly dry, adding water for dissolving, adjusting the pH value to be 1.5-2 by using sodium hydroxide, filtering, and performing cation resin exchange on the filtrate to obtain an exchange solution 2;
9) reduction:
continuously stirring, adding a sodium hydroxide solution into the exchange solution 2 obtained in the step 8), adjusting the pH value to 8-10, heating to boil, adding an 80% hydrazine hydrate solution, maintaining the temperature of 60-80 ℃ until the solution is clear and transparent, and completely reducing rhodium to obtain rhodium precipitate;
10) and (3) calcining:
filtering the rhodium precipitate obtained in the step 9), cleaning the rhodium precipitate with hot water to be neutral, putting the rhodium precipitate into a crucible, and calcining the rhodium precipitate for 20-40 minutes at 450-650 ℃ to obtain rhodium powder;
11) introducing hydrogen:
and (3) putting the rhodium powder obtained in the step 10) into a porcelain boat, putting the porcelain boat in a tube furnace, introducing hydrogen, keeping the temperature for 1-2 hours, continuously introducing the hydrogen, cooling the furnace to 300 ℃, and closing the hydrogen to obtain the high-purity rhodium powder with the purity of 99.99%.
2. The method of claim 1, wherein: the dosage of the sodium chloride solid in the step 1) is 0.5-0.7 time of the weight of the platinum rhodium waste.
3. The method of claim 1, wherein: the platinum-rhodium waste of step 1) is a failed platinum-rhodium alloy product with rhodium content less than 20%.
4. The method of claim 1, wherein: the concentration of the chlor-alkali in the step 1) and the step 2) is 5-20%.
5. The method of claim 1, wherein: and 3), 4) and 8) the sodium chloride solution is 5-15%.
6. The method of claim 1, wherein: the standing time of the steps 1), 2) and 4) is more than or equal to 5 hours.
7. The method of claim 1, wherein: step 3) and step 5) are carried out, wherein the rest time is 24 hours.
8. The method of claim 1, wherein: the concentration in the steps 1), 2) and 3) is only required to be that a crystal film appears on the liquid surface.
9. The method of claim 1, wherein: the washing precipitation of the steps 1), 2) and 4) is washing 3 times.
10. The method of claim 1, wherein: step 9) volume of hydrazine hydrate solution and rhodium: weight 1ml hydrazine hydrate: 1 g of rhodium.
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