CN113278813A - Method for separating and purifying rhodium in impurity-containing rhodium solution - Google Patents
Method for separating and purifying rhodium in impurity-containing rhodium solution Download PDFInfo
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Abstract
The invention discloses a method for separating and purifying rhodium in impurity-containing rhodium solution, which comprises the following process steps: s1, adjusting the acidity of the rhodium solution to 6-8 mol/L, and adding the prepared DETA solution to obtain a first filtrate; s2 adding aqua regia into the organic rhodium salt precipitate, heating to dissolve, adding hydrochloric acid to adjust the acidity of the solution to 6mol/L and the rhodium concentration to 50-80 g/L, heating to boil the solution, adding ammonium chloride to generate ammonium chlororhodate precipitate, and quickly filtering to obtain a filtrate II; adding zinc powder into the filtrate to replace rhodium ions in the rhodium solution; s3 passing through hydrogen type cation resin to remove trace metal impurity ions; s4 adding hydrazine hydrate to reduce and prepare rhodium black; and S5, combining the replacement slag, drying, and mixing the replacement slag with a mixture of 1: 1, soaking in hydrochloric acid to remove zinc and other metal impurities; s6 filtering, dissolving the filter residue with aqua regia, and returning the leaching solution to the purification process. The method has the characteristics of high direct yield, simple operation process and high purity, wherein qualified rhodium powder with the purity of more than 99.95 percent can be obtained after the rhodium black is reduced by introducing hydrogen.
Description
Technical Field
The invention relates to a method for extracting rhodium, in particular to a method for separating and purifying rhodium in an impurity-containing rhodium solution.
Background
The method for separating and purifying rhodium from the solution comprises a sodium nitrite complexation method, an ammoniation method, a potential control precipitation method, a hydrolysis method, a solvent extraction method and the like. The sodium nitrite complexation method is one of the most effective methods for removing base metal impurities in the rhodium solution, but the method has narrow material application range and long process; the ammonification method is based on the reaction of ammonium hexachlororhodate and ammonia water to generate pentammoniamonochloride-rhodium dichloride precipitate, but the method has complex operation process and lower rhodium recovery rate; the potential control precipitation method can adsorb rhodium in the process of precipitating platinum and palladium, thereby not only influencing the purity of the platinum and the palladium, but also influencing the recovery rate of the rhodium;
the hydrolysis method has wide application in rough separation of platinum and rhodium, and palladium generally exists in a solution in a Pd (II) form, so the rough separation of the platinum, the palladium and the rhodium by the hydrolysis method has difficulty; the technology of solvent extraction of rhodium has been studied more, but it is not applied to actual production.
Rhodium or Rh as sparingly soluble salts of aliphatic polyamines and trihydrohexahydrogermanic acid in noble metal refining processes3+Separated from other noble metals. Known representatives of said salts are the complex salts of Diethylenetriamine (DETA) and trihydrohexachlororhodic acid. It is also known to boil the salts of aliphatic polyamines and trihydrohexachlororhodic acid in aqua regia for further processing. In this process, the organic components are decomposed by oxidation and finally form an acidic aqueous solution of chlororhodic acid, which can be subjected to further refining. According to another known alternative, the aliphatic polyamine and the salt of trihydrohexahydrohalorhodium acid are calcined in an oxygen-containing atmosphere and the rhodium-containing oxidation residue is subjected to further refining.
In the patent (CN103343239B), a specially prepared triethylene tetramine solution is used for separating and purifying a rhodium solution, rhodium in the solution generates rhodium salt precipitate, and other precious and base metals cannot react with the prepared triethylene tetramine solution, so that the aim of separating the rhodium from other metals is fulfilled. The organic rhodium salt is calcined or reduced by introducing hydrogen to obtain rhodium powder with the purity of more than 99.9 percent. When the method is operated, the pH value of the solution is controlled to be 0.1-2.0, the operation temperature is 80-120 ℃, but the lower precipitation acidity can cause impurity metals to be entrained in rhodium salt precipitates, and the product purity is influenced. And the high-temperature operation of the solution increases the operation cost and labor intensity, and meanwhile, the organic rhodium salt precipitate is directly calcined, so that the possibility of loss of rhodium brought into flue gas along with the high-temperature calcination of organic components exists.
Patent (CN107406908A) describes that after preparing diethyltriammonium hexachlororhodate precipitate, adjusting pH between-1 and +2, rhodium salt suspension is prepared, and rhodium salt precipitate is prepared into sponge rhodium by using hydrazine, hydrazine hydrate, SnCl2, and non-noble metals such as zinc, iron, aluminum, tin and the like as reducing agents. In the actual operation process, hydrazine and hydrazine hydrate are used for reduction, the reaction is violent in the operation process, and the reaction is difficult to completely carry out. And metals such as zinc, iron, aluminum, tin and the like are used as reducing agents, new impurity elements are introduced, and the purity of the product is influenced.
In the patent (CN 104860358A), tetramethylammonium chloride is used as a precipitator, the concentration of a rhodium solution is controlled to be 30-80 g/L, a small amount of precipitator is added for reaction to remove high-valence impurities such as platinum, iron and the like, an excessive amount of precipitator is added into the obtained filtrate, and the filtrate is boiled and refluxed at 110-120 ℃ for 24-48 h to obtain rhodium salt precipitate. The rhodium salt precipitate is fully washed, dissolved, treated with resin and precipitated with potassium hydroxide to obtain high-purity rhodium hydroxide. However, platinum generally exists in a tetravalent state in the solution, palladium generally exists in a divalent state, and divalent palladium does not react with tetramethylammonium chloride, so that the method has limited separation and purification effects on rhodium solutions containing platinum and palladium impurities simultaneously, and cannot remove the influence of palladium. In addition, the operation time of the precipitation is long, the rhodium brown precipitate is generated after boiling and refluxing for 36 hours, and a sufficient amount of boiled water is needed for re-dissolution.
Aiming at the defects in the treatment process, the invention provides a method for separating and purifying rhodium in an impurity-containing rhodium solution.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: develops a method for separating and purifying rhodium in rhodium solution containing impurities, and has the characteristics of high direct yield, simple operation process and high purity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for separating and purifying rhodium in impurity-containing rhodium solution comprises the following process steps:
s1, adjusting the acidity of the rhodium solution to 6-8 mol/L, heating the rhodium solution to 60-80 ℃, slowly adding the prepared DETA solution while stirring, wherein the addition amount of the DETA solution is 8-10 times of the amount of the rhodium in the solution, a large amount of red precipitates are generated, and cooling, filtering and washing the precipitates to obtain a filtrate I;
s2 adding aqua regia into the organic rhodium salt precipitate, heating to dissolve, concentrating to a smaller volume, adding hydrochloric acid to adjust the acidity of the solution to 6mol/L and the rhodium concentration to 50-80 g/L, heating to boil the solution, adding ammonium chloride to generate ammonium chlororhodate precipitate, cooling to below 50 ℃, adding alcohol with the volume being 1-2 times that of the ammonium chlororhodate precipitate, reducing the solubility of the ammonium chlororhodate, and quickly filtering to obtain a filtrate II;
s3 dissolving the ammonium chlororhodate precipitate with water, controlling the pH of the solution to be 1-3, and removing trace metal impurity ions through hydrogen type cationic resin;
directly adding sodium hydroxide into the S4 exchange solution to adjust the pH value to 7-8, heating to boil, adding a hydrazine hydrate reducing agent to prepare rhodium black, and introducing hydrogen into the rhodium black to reduce to obtain qualified rhodium powder with the purity of more than 99.95%;
and S5, combining the replacement slag, drying, mixing with zinc powder uniformly according to the ratio of 1: 4-6, carrying out activation reaction in a muffle furnace at 700-900 ℃ for 4-6 h, cooling, taking out, and adding 1: 1, soaking in hydrochloric acid to remove zinc and other metal impurities;
s6 filtering, dissolving the filter residue with aqua regia, and returning the leaching solution to the purification process.
As a further improvement of the scheme, in S1, the filtrate I is added with reduced iron powder to replace rhodium ions in the filtrate. And adding reduced iron powder into the filtrate to replace rhodium ions in the filtrate. In the step S1, because a large amount of metal impurity ions are remained in the solution, zinc powder is not selected for replacement, and reduced iron powder is selected for replacing rhodium ions in the filtrate I, so that impurity metals are prevented from being replaced into replacement slag.
As a further improvement of the scheme, the DETA solution prepared in the S1 is prepared by 1.13Kg of deionized water, 3.56Kg of analytically pure hydrochloric acid and 1Kg of DETA.
As a further improvement of the scheme, zinc powder is added into the second filtrate in S2 to replace rhodium ions in the rhodium solution. And adding zinc powder into the filtrate II in the step S2 to replace rhodium ions in the rhodium solution. The solution has high purity and less impurity ions, and is replaced by zinc powder.
As a further improvement of the scheme, 1% hydrazine hydrate is also added as a protective agent when hydrochloric acid is added for soaking in S5. 1% hydrazine hydrate is added in S5 as a protective agent, so that trace rhodium can be effectively prevented from leaching.
Compared with the prior art, the invention has the beneficial effects that:
1) the acidity of DETA precipitate is adjusted to 6-8 mol/L, the temperature is adjusted to 60-80 ℃, metal impurity ions can be effectively reduced from being carried by rhodium salt precipitate under the strong acid condition, and meanwhile, the generated rhodium salt precipitate is large in specific gravity, obvious in granular feeling, not colloidal precipitate and easy to filter and rinse;
2) after the organic rhodium salt is precipitated and dissolved, the ammonium chloride is used for precipitating rhodium, impurities are further separated, the operation is convenient and quick compared with a tetramethylammonium chloride precipitation method, and meanwhile, the solubility of the ammonium chlororhodate can be effectively reduced and the direct recovery rate is improved by adding quantitative alcohol;
3) the ammonium chlororhodate is easy to dissolve in water, the acidity after dissolution is between 1 and 3, and impurity elements can be further removed directly through hydrogen type cationic resin, so that the purity is ensured;
4) the treatment method of the precipitation tail liquid is provided, the replacement slag is activated by zinc powder, so that the insoluble metal rhodium is improved in activity and can be leached by aqua regia, and the leachate can be returned to the purification process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described with reference to the following embodiments:
example 1
A method for separating and purifying rhodium in impurity-containing rhodium solution comprises the following process steps:
s1, adjusting the acidity of the rhodium solution to 6mol/L, heating the rhodium solution to 60-80 ℃, slowly adding the prepared DETA solution while stirring, wherein the addition amount of the DETA solution is 8 times of the rhodium amount in the solution, a large amount of red precipitates are generated, and cooling, filtering and washing to obtain a first filtrate; and adding reduced iron powder into the filtrate I in the S1 to replace rhodium ions in the filtrate. In the step S1, because a large amount of metal impurity ions are remained in the solution, zinc powder is not selected for replacement, and reduced iron powder is selected for replacing rhodium ions in the filtrate I, so that impurity metals are prevented from being replaced into replacement slag. Wherein, the prepared DETA solution is prepared by 1.13Kg of deionized water, 3.56Kg of analytically pure hydrochloric acid and 1Kg of DETA.
S2 adding aqua regia into the organic rhodium salt precipitate, heating to dissolve, concentrating to a smaller volume, adding hydrochloric acid to adjust the acidity of the solution to 6mol/L and the rhodium concentration to 50-80 g/L, heating to boil the solution, adding ammonium chloride to generate ammonium chlororhodate precipitate, cooling to below 50 ℃, adding alcohol with the volume being 1-2 times that of the ammonium chlororhodate precipitate, reducing the solubility of the ammonium chlororhodate, and quickly filtering to obtain a filtrate II; and (S2) adding zinc powder into the filtrate II to replace rhodium ions in the rhodium solution. And adding zinc powder into the filtrate II in the step S2 to replace rhodium ions in the rhodium solution. The solution has high purity and less impurity ions, and is replaced by zinc powder.
S3 dissolving the ammonium chlororhodate precipitate with water, controlling the pH of the solution to be 1-3, and removing trace metal impurity ions through hydrogen type cationic resin;
directly adding sodium hydroxide into the S4 exchange solution to adjust the pH value to 7-8, heating to boil, adding a hydrazine hydrate reducing agent to prepare rhodium black, and introducing hydrogen into the rhodium black to reduce to obtain qualified rhodium powder with the purity of more than 99.95%;
and S5, combining the replacement slag, drying, mixing with zinc powder uniformly according to the ratio of 1: 4-6, carrying out activation reaction in a muffle furnace at 700-900 ℃ for 4-6 h, cooling, taking out, and adding 1: 1, soaking in hydrochloric acid to remove zinc and other metal impurities; and when hydrochloric acid is added for soaking in S5, 1% hydrazine hydrate is also added as a protective agent. 1% hydrazine hydrate is added in S5 as a protective agent, so that trace rhodium can be effectively prevented from leaching.
S6 filtering, dissolving the filter residue with aqua regia, and returning the leaching solution to the purification process.
Example 2
A method for separating and purifying rhodium in impurity-containing rhodium solution comprises the following process steps:
s1, adjusting the acidity of the rhodium solution to 7mol/L, heating the rhodium solution to 60-80 ℃, slowly adding the prepared DETA solution while stirring, wherein the addition amount of the DETA solution is 9 times of the rhodium amount in the solution, a large amount of red precipitates are generated, and cooling, filtering and washing to obtain a first filtrate; and adding reduced iron powder into the filtrate I in the S1 to replace rhodium ions in the filtrate. In the step S1, because a large amount of metal impurity ions are remained in the solution, zinc powder is not selected for replacement, and reduced iron powder is selected for replacing rhodium ions in the filtrate I, so that impurity metals are prevented from being replaced into replacement slag. Wherein, the prepared DETA solution is prepared by 1.13Kg of deionized water, 3.56Kg of analytically pure hydrochloric acid and 1Kg of DETA.
S2 adding aqua regia into the organic rhodium salt precipitate, heating to dissolve, concentrating to a smaller volume, adding hydrochloric acid to adjust the acidity of the solution to 6mol/L and the rhodium concentration to 50-80 g/L, heating to boil the solution, adding ammonium chloride to generate ammonium chlororhodate precipitate, cooling to below 50 ℃, adding alcohol with the volume being 1-2 times that of the ammonium chlororhodate precipitate, reducing the solubility of the ammonium chlororhodate, and quickly filtering to obtain a filtrate II; and (S2) adding zinc powder into the filtrate II to replace rhodium ions in the rhodium solution. And adding zinc powder into the filtrate II in the step S2 to replace rhodium ions in the rhodium solution. The solution has high purity and less impurity ions, and is replaced by zinc powder.
S3 dissolving the ammonium chlororhodate precipitate with water, controlling the pH of the solution to be 1-3, and removing trace metal impurity ions through hydrogen type cationic resin;
directly adding sodium hydroxide into the S4 exchange solution to adjust the pH value to 7-8, heating to boil, adding a hydrazine hydrate reducing agent to prepare rhodium black, and introducing hydrogen into the rhodium black to reduce to obtain qualified rhodium powder with the purity of more than 99.95%;
and S5, combining the replacement slag, drying, mixing with zinc powder uniformly according to the ratio of 1: 4-6, carrying out activation reaction in a muffle furnace at 700-900 ℃ for 4-6 h, cooling, taking out, and adding 1: 1, soaking in hydrochloric acid to remove zinc and other metal impurities; and when hydrochloric acid is added for soaking in S5, 1% hydrazine hydrate is also added as a protective agent. 1% hydrazine hydrate is added in S5 as a protective agent, so that trace rhodium can be effectively prevented from leaching.
S6 filtering, dissolving the filter residue with aqua regia, and returning the leaching solution to the purification process.
Example 3
A method for separating and purifying rhodium in impurity-containing rhodium solution comprises the following process steps:
s1, adjusting the acidity of the rhodium solution to 8mol/L, heating the rhodium solution to 60-80 ℃, slowly adding the prepared DETA solution while stirring, wherein the addition amount of the DETA solution is 10 times of the rhodium amount in the solution, a large amount of red precipitates appear, and cooling, filtering and washing to obtain a first filtrate; and adding reduced iron powder into the filtrate I in the S1 to replace rhodium ions in the filtrate. In the step S1, because a large amount of metal impurity ions are remained in the solution, zinc powder is not selected for replacement, and reduced iron powder is selected for replacing rhodium ions in the filtrate I, so that impurity metals are prevented from being replaced into replacement slag. Wherein, the prepared DETA solution is prepared by 1.13Kg of deionized water, 3.56Kg of analytically pure hydrochloric acid and 1Kg of DETA.
S2 adding aqua regia into the organic rhodium salt precipitate, heating to dissolve, concentrating to a smaller volume, adding hydrochloric acid to adjust the acidity of the solution to 6mol/L and the rhodium concentration to 50-80 g/L, heating to boil the solution, adding ammonium chloride to generate ammonium chlororhodate precipitate, cooling to below 50 ℃, adding alcohol with the volume being 1-2 times that of the ammonium chlororhodate precipitate, reducing the solubility of the ammonium chlororhodate, and quickly filtering to obtain a filtrate II; and (S2) adding zinc powder into the filtrate II to replace rhodium ions in the rhodium solution. And adding zinc powder into the filtrate II in the step S2 to replace rhodium ions in the rhodium solution. The solution has high purity and less impurity ions, and is replaced by zinc powder.
S3 dissolving the ammonium chlororhodate precipitate with water, controlling the pH of the solution to be 1-3, and removing trace metal impurity ions through hydrogen type cationic resin;
directly adding sodium hydroxide into the S4 exchange solution to adjust the pH value to 7-8, heating to boil, adding a hydrazine hydrate reducing agent to prepare rhodium black, and introducing hydrogen into the rhodium black to reduce to obtain qualified rhodium powder with the purity of more than 99.95%;
and S5, combining the replacement slag, drying, mixing with zinc powder uniformly according to the ratio of 1: 4-6, carrying out activation reaction in a muffle furnace at 700-900 ℃ for 4-6 h, cooling, taking out, and adding 1: 1, soaking in hydrochloric acid to remove zinc and other metal impurities; and when hydrochloric acid is added for soaking in S5, 1% hydrazine hydrate is also added as a protective agent. 1% hydrazine hydrate is added in S5 as a protective agent, so that trace rhodium can be effectively prevented from leaching.
S6 filtering, dissolving the filter residue with aqua regia, and returning the leaching solution to the purification process.
TABLE 1 data for examples 1-3
From the data in examples 1-3 and Table 1 above, it can be seen that:
1) the acidity of DETA precipitate is adjusted to 6-8 mol/L, the temperature is adjusted to 60-80 ℃, metal impurity ions can be effectively reduced from being carried by rhodium salt precipitate under the strong acid condition, and meanwhile, the generated rhodium salt precipitate is large in specific gravity, obvious in granular feeling, not colloidal precipitate and easy to filter and rinse;
2) after the organic rhodium salt is precipitated and dissolved, the ammonium chloride is used for precipitating rhodium, impurities are further separated, the operation is convenient and quick compared with a tetramethylammonium chloride precipitation method, meanwhile, the solubility of the ammonium chloride and rhodium can be effectively reduced by adding quantitative alcohol, the direct yield is improved, and the yield is as high as 96.78%;
3) the ammonium chlororhodate is easy to dissolve in water, the acidity after dissolution is between 1 and 3, and impurity elements can be further removed directly through hydrogen type cationic resin, so that the purity is ensured;
4) the treatment method of the precipitation tail liquid is provided, the replacement slag is activated by zinc powder, so that the insoluble metal rhodium is improved in activity and can be leached by aqua regia, and the leachate can be returned to the purification process.
The above description is only for the preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention are within the scope of the present invention.
Claims (5)
1. A separation and purification method of rhodium in impurity-containing rhodium solution is characterized by comprising the following process steps:
s1, adjusting the acidity of the rhodium solution to 6-8 mol/L, heating the rhodium solution to 60-80 ℃, slowly adding the prepared DETA solution while stirring, wherein the addition amount of the DETA solution is 8-10 times of the amount of the rhodium in the solution, a large amount of red precipitates are generated, and cooling, filtering and washing the precipitates to obtain a filtrate I;
s2 adding aqua regia into the organic rhodium salt precipitate, heating to dissolve, concentrating to a smaller volume, adding hydrochloric acid to adjust the acidity of the solution to 6mol/L and the rhodium concentration to 50-80 g/L, heating to boil the solution, adding ammonium chloride to generate ammonium chlororhodate precipitate, cooling to below 50 ℃, adding alcohol with the volume being 1-2 times that of the ammonium chlororhodate precipitate, reducing the solubility of the ammonium chlororhodate, and quickly filtering to obtain a filtrate II;
s3 dissolving the ammonium chlororhodate precipitate with water, controlling the pH of the solution to be 1-3, and removing trace metal impurity ions through hydrogen type cationic resin;
directly adding sodium hydroxide into the S4 exchange solution to adjust the pH value to 7-8, heating to boil, adding hydrazine hydrate to reduce to obtain rhodium black, and introducing hydrogen into the rhodium black to reduce to obtain qualified rhodium powder with the purity of more than 99.95%;
and S5, combining the replacement slag, drying, mixing with zinc powder uniformly according to the ratio of 1: 4-6, carrying out activation reaction in a muffle furnace at 700-900 ℃ for 4-6 h, cooling, taking out, and adding 1: 1, soaking in hydrochloric acid to remove zinc and other metal impurities;
s6 filtering, dissolving the filter residue with aqua regia, and returning the leaching solution to the purification process.
2. The method for separating and purifying rhodium in rhodium-containing solution as impurity according to claim 1, wherein in S1, reduced iron powder is added into the first filtrate to replace rhodium ions in the filtrate.
3. The method for separating and purifying rhodium in rhodium-containing solution containing impurities according to claim 1, wherein DETA solution prepared in S1 is prepared from 1.13Kg of deionized water, 3.56Kg of analytically pure hydrochloric acid, and 1Kg of DETA.
4. The method for separating and purifying rhodium in rhodium solution containing impurities as claimed in claim 1, wherein zinc powder is added into the second filtrate in S2 to replace rhodium ions in the rhodium solution.
5. The method for separating and purifying rhodium in rhodium-containing solution as impurities of claim 1, wherein 1% hydrazine hydrate is further added as a protective agent during the soaking in hydrochloric acid in S5.
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| CN113832356A (en) * | 2021-09-27 | 2021-12-24 | 格林美股份有限公司 | Method for separating and purifying rhodium in high-iron rhodium-containing feed liquid |
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| CN114346251A (en) * | 2021-12-23 | 2022-04-15 | 江西省汉氏贵金属有限公司 | Preparation method of rhodium powder |
| CN115011807A (en) * | 2022-06-14 | 2022-09-06 | 英特派铂业股份有限公司 | Purification method for efficiently separating rhodium and iridium with high yield |
| CN115536082A (en) * | 2022-11-04 | 2022-12-30 | 郴州高鑫材料有限公司 | Method for preparing rhodium trichloride and ammonium chloroiridate from rhodium-iridium/silica gel adsorbent |
| CN117210694A (en) * | 2023-11-09 | 2023-12-12 | 云南贵金属实验室有限公司 | Method for enriching and recovering noble metal from rhodium-precipitated DETA solution |
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