CN115849586A - Method for recovering rhodium from rhodium-containing wastewater and recovered rhodanate - Google Patents
Method for recovering rhodium from rhodium-containing wastewater and recovered rhodanate Download PDFInfo
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- CN115849586A CN115849586A CN202111106373.3A CN202111106373A CN115849586A CN 115849586 A CN115849586 A CN 115849586A CN 202111106373 A CN202111106373 A CN 202111106373A CN 115849586 A CN115849586 A CN 115849586A
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- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 133
- 239000010948 rhodium Substances 0.000 title claims abstract description 133
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000002351 wastewater Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000010992 reflux Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000012530 fluid Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- 239000002535 acidifier Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 claims abstract description 6
- YQTPVZDDJNOGNJ-UHFFFAOYSA-N rhodium hydrochloride Chemical compound Cl.[Rh] YQTPVZDDJNOGNJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 235000010288 sodium nitrite Nutrition 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 17
- 238000003756 stirring Methods 0.000 description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- -1 rhodium ions Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering rhodium from rhodium-containing wastewater and a recovered rhodium hydrochloride, and relates to the technical field of rhodium recovery. The method for recovering rhodium from rhodium-containing wastewater comprises the following steps: concentrating the rhodium-containing wastewater, adding an acidifying agent into the concentrated rhodium-containing wastewater to adjust the pH value, and then heating and refluxing to obtain an acidified solution; adding a complexing agent into the acidized fluid for reaction, and filtering to obtain rhodium-containing filtrate; adding a precipitator into the rhodium-containing filtrate for reaction, and filtering to obtain a rhodium-containing filter cake; dissolving the rhodium-containing filter cake with acid A to obtain a rhodanate solution; adding alkali liquor to adjust the pH value, performing precipitation reaction, and performing post-treatment to obtain rhodium hydroxide; and dissolving the rhodium hydroxide by using acid B to prepare a rhodium hydrochloride solution. The method for recovering rhodium from rhodium-containing wastewater has the advantages of low rhodium loss rate, high rhodium recovery rate of more than 97.07 percent, simple process, strong selectivity, low cost, high recovery rate and the like.
Description
Technical Field
The invention relates to the technical field of rhodium recovery, and further relates to a method for recovering rhodium from rhodium-containing wastewater and a recovered rhodate.
Background
Rhodium is used as a very expensive noble metal, has very wide application in the field of petrochemical industry, particularly in the field of carbonyl synthesis of hydroformylation of olefins, and has very important application and large demand. Therefore, the domestic rhodium recovery work has great economic and social benefits.
A large amount of rhodium-containing waste water is generated in the oxo reaction and the recovery process of waste rhodium catalyst raffinate, and the rhodium-containing waste water usually has low rhodium content and a large amount of impurities and is very difficult to treat.
At present, the treatment method of precious metal wastewater in the world usually adopts physical methods and chemical methods, including ion exchange methods, precipitation methods, adsorption methods and the like, wherein the ion exchange methods achieve the purpose of separating and recovering rhodium based on ion exchange, are simple to operate and have large treatment capacity, so the ion exchange methods are widely applied to metal recovery, but the resins used in the ion exchange methods are expensive and difficult to regenerate, and new pollution is easily generated.
The precipitation separation method can be used for extracting and recovering rhodium by a direct precipitation method, has the characteristics of simple process, convenience in operation and the like, but needs to control conditions to ensure the recovery rate and the purity, and has a narrow application range.
Disclosure of Invention
In order to solve the problem of low rhodium recovery rate in the prior art, the invention provides a method for recovering rhodium from rhodium-containing wastewater and a recovered rhodanate. The method for recovering rhodium from rhodium-containing wastewater has the characteristics of low rhodium loss rate, high rhodium recovery rate of more than 97.07 percent, simple process, strong selectivity, low cost, high recovery rate and the like.
One of the purposes of the invention is to provide a method for recovering rhodium from rhodium-containing wastewater, which comprises the following steps:
(1) Concentrating the rhodium-containing wastewater, adding an acidifying agent into the concentrated rhodium-containing wastewater to adjust the pH value, and then heating and refluxing to obtain an acidifying solution;
(2) Adding a complexing agent into the acidizing fluid for reaction, and filtering to obtain a rhodium-containing filtrate;
(3) Adding a precipitator into the rhodium-containing filtrate for reaction, and filtering to obtain a rhodium-containing filter cake;
(4) Dissolving the rhodium-containing filter cake with acid A to obtain a rhodanate solution; adding alkali liquor to adjust the pH value, performing precipitation reaction, and performing post-treatment to obtain rhodium hydroxide;
(5) And dissolving the rhodium hydroxide by using acid B to prepare a rhodium hydrochloride solution.
Preferably, the first and second liquid crystal materials are,
in the step (1), the step (c),
after the rhodium-containing wastewater is concentrated, the content of rhodium is 2-3 g/L;
the concentration mode comprises reduced pressure distillation.
Preferably, the first and second liquid crystal materials are,
in the step (1), the raw material is processed,
the acidifying agent comprises concentrated hydrochloric acid, and the acidifying agent is added until the pH value of the solution is less than or equal to 1.2, and the pH value is preferably 1-1.2;
in the present invention, in the step (1), the temperature and time of the heating reflux process are not particularly limited so that the reaction in the step (1) can be completed sufficiently.
In a preferred embodiment of the method of the invention,
the heating reflux temperature is 80-100 ℃, and the reflux time is 2-4 hours.
Preferably, the first and second liquid crystal materials are,
in the step (2),
the complexing agent is selected from sodium nitrite solution;
the complexing agent is added into the acidizing fluid in a dropwise manner, and no new precipitate is generated when the complexing agent is added into the system.
Preferably, the first and second liquid crystal materials are,
in the step (2),
the concentration of the sodium nitrite solution is 30-40 wt%;
before the complexing agent is added into the acidizing fluid, the pH value of the acidizing fluid needs to be kept between 1 and 1.5;
in the invention, if the pH value of the acidizing fluid in the step (1) is 1-1.2, a complexing agent can be directly added at the moment; if the pH value of the acidizing fluid in the step (1) is less than 1, a little sodium hydroxide is added before the complexing agent is added in the step (2), so that the pH value of the acidizing fluid is preferably kept between 1 and 1.5.
In the invention, in the step (2), the temperature and time of the heating reflux process have no special requirements, so that the reaction in the step (2) can be fully completed.
Preferably, the first and second liquid crystal materials are,
the reaction is carried out under heating reflux at 80-100 deg.C, and the heating is stopped when the pH value is 6-6.5.
In a preferred embodiment of the method of the invention,
in the step (3), the step (c),
the precipitating agent is selected from ammonium chloride;
the mass ratio of the precipitating agent to rhodium element in the rhodium-containing filtrate is (2.1-3.5);
the reaction temperature is 18-25 ℃.
Preferably, the first and second liquid crystal materials are,
in the step (4), the step (c),
the acid A comprises concentrated hydrochloric acid and/or dilute sulfuric acid, and the concentration of the dilute sulfuric acid is preferably 10-30wt%.
In a preferred embodiment of the method of the invention,
in the step (4), the step (c),
the alkali liquor is selected from sodium hydroxide solution;
the concentration of the alkali liquor is 20-30 wt%;
adjusting the pH value to 8.5-9.5.
Preferably, the first and second liquid crystal materials are,
in the step (5), the first step is that,
the acid B is selected from concentrated hydrochloric acid.
It is a further object of the invention to provide the rhodates recovered by the process of one of the objects of the invention.
Compared with the traditional recovery method, the invention has the following beneficial effects:
according to the method for recovering rhodium, the steps of adding the complexing agent, the precipitating agent and the like are adopted, so that rhodium ions can be recovered in a targeted manner, and the method has the characteristic of strong selectivity.
The method for recovering rhodium is applied to the recovery of rhodium-containing wastewater, and has the characteristics of simple process, strong selectivity, low cost, high recovery rate and the like.
The invention provides a method for recovering rhodium from rhodium-containing wastewater, which comprises the steps of firstly concentrating the rhodium-containing wastewater, then acidifying, heating and refluxing to remove organic matters. Then adding a complexing agent for complexing, and separating from other metals. Then adding a precipitator for sedimentation and then purifying to obtain pure rhodium-containing solution. The method for recovering rhodium has the advantages of simple operation, high efficiency and low rhodium loss, and the yield of rhodium is more than 97.07 percent.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the examples and comparative examples are, if not particularly limited, those disclosed in the prior art, and may be, for example, obtained as they are or prepared according to the production methods disclosed in the prior art.
The rhodium yield is calculated by the following formula:
rhodium yield = (mass of chlororhodic acid solution x rhodium-containing concentration)/(concentration of rhodium in rhodium-containing wastewater x mass of wastewater) × 100%
The rhodium concentration in the rhodium-containing solution was analyzed by ICP.
Example 1
Carrying out reduced pressure distillation on the rhodium-containing wastewater, concentrating until the rhodium content of the rhodium-containing wastewater is 2g/L, adding concentrated hydrochloric acid to adjust the pH value of the solution to 1, and heating and refluxing for 2 hours at the temperature of 90 ℃; preparing an acidizing fluid, gradually dropwise adding a sodium nitrite solution with the concentration of 40wt% into the acidizing fluid under the stirring condition, and adding the acidizing fluid into the system without generating new precipitates; stirring and refluxing for reaction, heating and refluxing at 90 ℃, stopping heating when the reaction reaches a pH value of 6.5, cooling to room temperature, filtering, washing filter cakes after filtering, and combining filtrate to obtain rhodium-containing filtrate; adding ammonium chloride powder (ammonium chloride: rhodium element mass ratio is 2.1).
Example 2
Carrying out reduced pressure distillation on the rhodium-containing wastewater, concentrating until the rhodium content of the rhodium-containing wastewater is 3g/L, adding concentrated hydrochloric acid to adjust the pH value of the solution to 1, heating and refluxing for 4 hours at the temperature of 80 ℃ to prepare an acidified solution, gradually dropwise adding a sodium nitrite solution with the concentration of 40wt% into the acidified solution under the condition of stirring, reacting under stirring and refluxing, heating and refluxing at the temperature of 80 ℃, stopping heating when the pH value is 6.5, cooling to room temperature, filtering, washing filter cakes after filtering, and combining filtrate to prepare rhodium-containing filtrate; adding ammonium chloride powder (ammonium chloride: rhodium element mass ratio is 2.5).
Example 3
Carrying out reduced pressure distillation on the rhodium-containing wastewater, concentrating until the rhodium content of the rhodium-containing wastewater is 2.5g/L, adding concentrated hydrochloric acid to adjust the pH value of the solution to 1.2, heating and refluxing for 3 hours, heating and refluxing at 90 ℃, gradually dropwise adding a sodium nitrite solution with the concentration of 40wt% into an acidizing solution under the stirring condition, reacting under the stirring and refluxing conditions, heating and refluxing at 90 ℃, stopping heating when the pH value is 6.5 after the reaction, cooling to room temperature, filtering, washing a filter cake after the filtering, and combining the filtrate to obtain a rhodium-containing filtrate; adding ammonium chloride powder (ammonium chloride: rhodium element mass ratio is 2.8.
Example 4
Carrying out reduced pressure distillation on the rhodium-containing wastewater, concentrating until the rhodium content of the rhodium-containing wastewater is 2g/L, adding concentrated hydrochloric acid to adjust the pH value of the solution to 1.2, heating and refluxing for 2 hours at the temperature of 100 ℃, gradually dropwise adding a sodium nitrite solution with the concentration of 30wt% into the acidizing solution under the condition of stirring, reacting under the condition of stirring and refluxing, heating and refluxing at the temperature of 100 ℃, stopping heating when the pH value is 6.5 after the reaction, cooling to room temperature, filtering, washing filter cakes after filtering, and combining filtrate to obtain rhodium-containing filtrate; adding ammonium chloride powder (ammonium chloride: rhodium element mass ratio is 3.
Example 5
Carrying out reduced pressure distillation on the rhodium-containing wastewater, concentrating until the rhodium content of the rhodium-containing wastewater is 2.7g/L, adding concentrated hydrochloric acid to adjust the pH value of the solution to 1.1, heating and refluxing for 3.5 hours at the temperature of 90 ℃, gradually dropwise adding a 35wt% sodium nitrite solution into the acidizing fluid under the condition of stirring, reacting under stirring and refluxing, heating and refluxing at the temperature of 90 ℃, stopping heating when the pH value is 6.5 after the reaction, cooling to room temperature, filtering, washing filter cakes after filtering, and combining the filtrate to obtain a rhodium-containing filtrate; adding ammonium chloride powder (ammonium chloride: rhodium element mass ratio is 3.5).
Example 6
Carrying out reduced pressure distillation on the rhodium-containing wastewater, concentrating until the rhodium content of the rhodium-containing wastewater is 2.7g/L, adding concentrated hydrochloric acid to adjust the pH value of the solution to 1.1, heating and refluxing for 3 hours, heating and refluxing at the temperature of 95 ℃, gradually dropwise adding a sodium nitrite solution with the concentration of 35wt% into an acidizing solution under the stirring condition, reacting under stirring and refluxing, heating and refluxing at the temperature of 95 ℃, stopping heating when the reaction is carried out until the pH value is 6, cooling to room temperature, filtering, washing a filter cake after filtering, and combining filtrate to obtain rhodium-containing filtrate; adding ammonium chloride powder (ammonium chloride: rhodium element mass ratio is 3.2).
Comparative example 1
It is the same as the preparation process of example 5 except that the step of concentrating the rhodium-containing wastewater is not included.
The rhodium recovery rate of the chlororhodic acid solution prepared by the method is 90.14 percent.
Comparative example 2
It is the same as the preparation process of example 5, except that the rhodium-containing waste water is concentrated to a rhodium content of 4g/L.
The rhodium recovery rate of the chlororhodic acid solution prepared by the method is 94.32 percent.
Comparative example 3
The preparation method is the same as that of the example 5, except that the pH of the solution is adjusted to 2 by adding concentrated hydrochloric acid into the rhodium-containing wastewater after concentration, and the sodium nitrite solution with the same concentration as that of the example 5 is directly added dropwise after refluxing under the condition of pH 2.
The rhodium recovery rate of the chlororhodic acid solution prepared by the method is 95.77 percent.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for recovering rhodium from rhodium-containing wastewater is characterized by comprising the following steps:
(1) Concentrating the rhodium-containing wastewater, adding an acidifying agent into the concentrated rhodium-containing wastewater to adjust the pH value, and then heating and refluxing to obtain an acidifying solution;
(2) Adding a complexing agent into the acidized fluid for reaction, and filtering to obtain rhodium-containing filtrate;
(3) Adding a precipitator into the rhodium-containing filtrate for reaction, and filtering to obtain a rhodium-containing filter cake;
(4) Dissolving a rhodium-containing filter cake with acid A to obtain a rhodium hydrochloride solution; adding alkali liquor to adjust the pH value, performing precipitation reaction, and performing post-treatment to obtain rhodium hydroxide;
(5) And dissolving the rhodium hydroxide by using acid B to prepare a rhodium hydrochloride solution.
2. The method for recovering rhodium from rhodium-containing wastewater according to claim 1,
in the step (1), the raw material is processed,
after the rhodium-containing wastewater is concentrated, the content of rhodium is 2-3 g/L;
the concentration mode comprises reduced pressure distillation.
3. The method for recovering rhodium from rhodium-containing wastewater according to claim 1,
in the step (1), the step (c),
the acidifying agent comprises concentrated hydrochloric acid, and the acidifying agent is added until the pH value of the solution is less than or equal to 1.2, and the pH value is preferably 1-1.2;
the heating reflux temperature is 80-100 ℃, and the reflux time is 2-4 hours.
4. The method according to claim 1, wherein the rhodium is recovered from the rhodium-containing wastewater,
in the step (2),
the complexing agent is selected from sodium nitrite solution;
the complexing agent is added into the acidizing fluid in a dropwise manner, and no new precipitate is generated when the complexing agent is added into the system.
5. The method according to claim 4, wherein the rhodium is recovered from the rhodium-containing wastewater,
in the step (2), the step (3),
the concentration of the sodium nitrite solution is 30-40 wt%;
before the complexing agent is added into the acidizing fluid, the pH value of the acidizing fluid needs to be kept between 1 and 1.5;
the reaction is carried out under heating reflux at 80-100 deg.C, and the heating is stopped when the pH value is 6-6.5.
6. The method for recovering rhodium from rhodium-containing wastewater according to claim 1,
in the step (3), the step (c),
the precipitating agent is selected from ammonium chloride;
the mass ratio of the precipitating agent to rhodium element in the rhodium-containing filtrate is 2.1-3.5;
the reaction temperature is 18-25 ℃.
7. The method for recovering rhodium from rhodium-containing wastewater according to claim 1,
in the step (4), the step (C) is carried out,
the acid A comprises concentrated hydrochloric acid and/or dilute sulfuric acid, and the concentration of the dilute sulfuric acid is preferably 10-30wt%.
8. The method for recovering rhodium from rhodium-containing wastewater according to claim 1,
in the step (4), the step (c),
the alkali liquor is selected from sodium hydroxide solution;
the concentration of the alkali liquor is 20-30 wt%;
adjusting the pH value to 8.5-9.5.
9. The method for recovering rhodium from rhodium-containing wastewater according to claim 1,
in the step (5), the step (c),
the acid B is selected from concentrated hydrochloric acid.
10. A rhodium acid salt recovered according to the process of any one of claims 1 to 9.
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| JP2012031449A (en) * | 2010-07-29 | 2012-02-16 | National Institute Of Advanced Industrial Science & Technology | Method for recovering rhodium |
| CN102586607A (en) * | 2012-03-06 | 2012-07-18 | 张桂香 | Method for extracting platinum, rhodium and palladium from failed platinum alloy gauze |
| CN102910720A (en) * | 2012-11-22 | 2013-02-06 | 西南化工研究设计院有限公司 | Recovery process of rhodium-containing waste catalyst solution |
| CN105463202A (en) * | 2015-12-09 | 2016-04-06 | 中国海洋石油总公司 | Method for preparing high-purity rhodium chloride by removing impurities from impurity-containing chlororhodic acid solution |
| CN112537808A (en) * | 2020-12-07 | 2021-03-23 | 金川集团股份有限公司 | Method for synthesizing rhodium nitrate solution by using rhodium-containing waste |
| CN113199033A (en) * | 2021-05-18 | 2021-08-03 | 安徽拓思贵金属有限公司 | Preparation method of high-purity rhodium powder |
-
2021
- 2021-09-22 CN CN202111106373.3A patent/CN115849586A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012031449A (en) * | 2010-07-29 | 2012-02-16 | National Institute Of Advanced Industrial Science & Technology | Method for recovering rhodium |
| CN102586607A (en) * | 2012-03-06 | 2012-07-18 | 张桂香 | Method for extracting platinum, rhodium and palladium from failed platinum alloy gauze |
| CN102910720A (en) * | 2012-11-22 | 2013-02-06 | 西南化工研究设计院有限公司 | Recovery process of rhodium-containing waste catalyst solution |
| CN105463202A (en) * | 2015-12-09 | 2016-04-06 | 中国海洋石油总公司 | Method for preparing high-purity rhodium chloride by removing impurities from impurity-containing chlororhodic acid solution |
| CN112537808A (en) * | 2020-12-07 | 2021-03-23 | 金川集团股份有限公司 | Method for synthesizing rhodium nitrate solution by using rhodium-containing waste |
| CN113199033A (en) * | 2021-05-18 | 2021-08-03 | 安徽拓思贵金属有限公司 | Preparation method of high-purity rhodium powder |
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