CN112111659B - Method for recovering rhodium from rhodium-containing waste liquid - Google Patents
Method for recovering rhodium from rhodium-containing waste liquid Download PDFInfo
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- CN112111659B CN112111659B CN202011024493.4A CN202011024493A CN112111659B CN 112111659 B CN112111659 B CN 112111659B CN 202011024493 A CN202011024493 A CN 202011024493A CN 112111659 B CN112111659 B CN 112111659B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The invention provides a method for recovering rhodium in rhodium-containing waste liquid, which comprises the following steps: concentrating the rhodium-containing waste liquid to prepare a concentrated solution; the weight percentage of rhodium in the concentrated solution is not lower than 1%; and adding nitrite and hydrazine hydrate into the concentrated solution to react, and collecting solid. The recovery method has high recovery rate of rhodium in the rhodium-containing waste liquid, and the recovered rhodium-containing product has high purity.
Description
Technical Field
The invention relates to the technical field of metal recovery, in particular to a method for recovering rhodium in rhodium-containing waste liquid.
Background
Among the platinum group metals, metal rhodium is increasingly used in the field of organic synthesis due to its specific electrochemical properties and excellent catalytic properties. Rhodium can receive a plurality of different complexes to form special spatial structures, and therefore can be applied to the field of chemical catalysis. Conventional homogeneous rhodium catalysts may be, for example, triphenylphosphine rhodium chloride, rhodium acetylacetonate carbonyl, and the like. The triphenylphosphine rhodium chloride can be used as a hydrogenation catalyst, an aldehyde decarbonylation reaction catalyst, a partial substitution reaction catalyst of propylene, and reaction catalysts for oxidation, isomerization, carbonylation or hydrosilation and the like; rhodium acetylacetonate carbonyl can be used as a catalyst for oxo synthesis, a catalyst for hydroformylation of olefins, and the like.
In the process of preparing the homogeneous rhodium catalyst, due to certain chemical properties of rhodium, a series of problems that intermediate products and products are decomposed or the products cannot be completely separated from reaction liquid exist, so that the conversion rate of rhodium is low, a large amount of rhodium does not enter the homogeneous rhodium catalyst product in mother liquid, after the actually prepared homogeneous rhodium catalyst is separated, a considerable part of rhodium exists in reaction waste liquid, and a recovery method needs to be developed for recovery. The method directly utilizes the reduction method to recover the metal rhodium in the rhodium-containing waste liquid, and also adopts the complexing purification method to recover the metal rhodium in the rhodium-containing waste liquid. However, the recovery rate and the product purity of the method are both improved.
Disclosure of Invention
Therefore, a method for recovering rhodium from the rhodium-containing waste liquid is needed, and the recovery method has high recovery rate of rhodium in the rhodium-containing waste liquid and high purity of the recovered rhodium-containing product.
A method for recovering rhodium in rhodium-containing waste liquid comprises the following steps:
concentrating the rhodium-containing waste liquid to prepare a concentrated solution; the weight percentage of rhodium in the concentrated solution is not lower than 1%;
and adding nitrite and hydrazine hydrate into the concentrated solution to react, and collecting solid.
In one embodiment, the molar ratio of the nitrite to rhodium in the rhodium-containing waste stream is 10: 1-1: 1.
in one embodiment, the molar ratio of the nitrite to rhodium in the rhodium-containing waste stream is 4: 1-2: 1.
in one embodiment, the molar ratio of the hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 0.5: 1-10: 1.
in one embodiment, the molar ratio of the hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 3: 1-1: 1.
in one embodiment, the redox reaction is carried out at 60-120 ℃ for 2-12 h.
In one embodiment, the redox reaction is carried out at 65-75 ℃ for 8-12 h.
In one embodiment, the rhodium sulfate is prepared by dissolving the solid in sulfuric acid.
In one embodiment, the rhodium-containing waste liquid is a waste liquid for preparing a rhodium-containing homogeneous catalyst.
In one embodiment, the homogeneous catalyst is triphenylphosphine rhodium chloride or rhodium acetylacetonate carbonyl.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for recovering rhodium from the rhodium-containing waste liquid, nitrite and hydrazine hydrate are added into the rhodium-containing waste liquid, wherein the nitrite oxidizes the rhodium-containing waste liquid to destroy the compatibility structure of rhodium, and then the rhodium is purified by reducing with the hydrazine hydrate, so that the rhodium in the waste liquid can be recovered at a high recovery rate, and the prepared product has high purity and can be used as a raw material of a rhodium-containing homogeneous catalyst.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a method for recovering rhodium in rhodium-containing waste liquid, which comprises the following steps:
concentrating the rhodium-containing waste liquid to prepare a concentrated solution; the weight percentage of rhodium in the concentrated solution is not lower than 1%;
and adding nitrite and hydrazine hydrate into the concentrated solution to react, and collecting solid.
It is understood that the rhodium-containing waste liquid refers to a waste liquid containing rhodium ions, complexes of rhodium, or other rhodium in an optional form. Generally, rhodium in rhodium-containing waste liquid exists in a plurality of valence states, the nitrite is used for oxidizing the rhodium to a valence state of 3, and is also used as an oxidizing agent for oxidizing phosphorus-containing groups in the material, so that the complexation of the rhodium and P is eliminated, alkalinity is provided, the rhodium is formed into rhodium hydroxide, and hydroxide radicals are provided for reducing hydrazine hydrate.
In one specific embodiment, the rhodium-containing waste liquid is a waste liquid from the preparation of a rhodium-coordinated homogeneous catalyst. More specifically, the rhodium-coordinated homogeneous catalyst refers to triphenylphosphine rhodium chloride or acetylacetonatocarbonylrhodium.
In one specific embodiment, the weight percentage of rhodium in the concentrated solution can be controlled to be 1-10%.
In one specific embodiment, the molar ratio of the nitrite to rhodium in the rhodium-containing waste liquid is 10: 1-1: 1. the molar ratio of the nitrite to the rhodium in the rhodium-containing waste liquid is reasonably regulated, so that the low-valence rhodium can be completely oxidized into the 3-valence rhodium, the rhodium is favorably separated from a coordination structure, and the recovery rate is improved. Further, the molar ratio of the nitrite to rhodium in the rhodium-containing waste liquid is 4: 1-2: 1.
in one specific embodiment, the molar ratio of the hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 0.5: 1-10: 1. the molar ratio of the hydrazine hydrate to the rhodium in the rhodium-containing waste liquid is reasonably regulated, so that the 3-valent rhodium can be pertinently reduced, the purification of the rhodium is facilitated, and a high-purity product is prepared and is directly used for preparing the rhodium-containing homogeneous catalyst. Further, the molar ratio of the hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 3: 1-1: 1.
in one specific embodiment, the redox reaction is carried out at 60-120 ℃ for 2-12 h. The reaction conditions of the oxidation-reduction reaction are reasonably controlled, the oxidation reaction and the reduction purification can be completed by a one-pot method, the working procedures are simplified, the production efficiency is improved, the reaction conversion rate is ensured, and the recovery rate is improved. Preferably, the redox reaction is carried out for 8-12 hours at the temperature of 65-75 ℃.
Further, in one specific example, rhodium sulfate is prepared by dissolving the solid in sulfuric acid. The prepared rhodium sulfate can be directly used for preparing a rhodium-containing homogeneous catalyst.
Hereinafter, specific examples are described, and the raw materials used in the examples are all commercially available unless otherwise specified.
Example 1
The embodiment is a method for recovering rhodium in rhodium-containing waste liquid, comprising the following steps:
(1) 1000 liters of waste liquid for preparing triphenylphosphine rhodium chloride (wherein the weight percentage of rhodium is 0.1 percent) is concentrated to the weight percentage of rhodium of 1.2 percent (wherein, the molar weight of rhodium is calculated to be 9.6 mol);
(2) adding 2kg of sodium nitrite (29mol) and 2.3kg of hydrazine hydrate aqueous solution (mass concentration is 50%, and hydrazine hydrate is 23mol) into the concentrated solution obtained in the step (1), heating to 70 ℃, stirring for 10 hours, and filtering the obtained reactant to obtain 989 g of black powder;
(3) adding 10L of concentrated sulfuric acid into the black powder to obtain a rhodium sulfate solution; the calculated recovery rate was 99%.
Example 2
The embodiment is a method for recovering rhodium in rhodium-containing waste liquid, comprising the following steps:
(1) 1000 liters of waste liquid for preparing acetylacetonatocarbonylrhodium (wherein the concentration of rhodium is 56.7ppm) is concentrated to the weight percentage of rhodium of 1.1 percent (wherein, the molar weight of rhodium is calculated to be 0.55 mol);
(2) adding 100g of sodium nitrite (1.45mol) and 110g of hydrazine hydrate aqueous solution (mass concentration is 50%, and hydrazine hydrate content is 1.1mol) into the concentrated solution obtained in the step (1), heating to 70 ℃, stirring for 10 hours, and filtering the obtained reactant to obtain 55 g of black powder;
(3) adding 10L of concentrated sulfuric acid into the black powder to obtain a rhodium sulfate solution; the check recovery rate is 97%.
Comparative example 1
The comparative example is a method for recovering rhodium from rhodium-containing waste liquid, and the steps are the same as those of the example 1, except that: in the step (2), only hydrazine hydrate is added for reaction.
The method comprises the following specific steps:
(1) 1000 liters of waste liquid for preparing triphenylphosphine rhodium chloride (wherein the weight percentage of rhodium is 0.1 percent) is concentrated to the weight percentage of rhodium of 1.2 percent (wherein, the molar weight of rhodium is calculated to be 9.6 mol);
(2) adding 2.3kg of hydrazine hydrate aqueous solution (the mass concentration is 50 percent, and the hydrazine hydrate content is 23mol) into the concentrated solution obtained in the step (1), heating to 70 ℃, stirring for 10 hours, and filtering the obtained reaction product to obtain 0g of black powder; the check recovery rate was 0%.
Comparative example 2
The comparative example is a method for recovering rhodium from rhodium-containing waste liquid, and the steps are the same as those of the example 1, except that: in the step (2), only sodium nitrite is added for reaction.
The method comprises the following specific steps:
(1) 1000 liters of waste liquid for preparing triphenylphosphine rhodium chloride (wherein the weight percentage of rhodium is 0.1 percent) is concentrated to the weight percentage of rhodium of 1.2 percent (wherein, the molar weight of rhodium is calculated to be 9.6 mol);
(2) adding 2kg of sodium nitrite (29mol) into the concentrated solution obtained in the step (1), heating to 70 ℃, stirring for 10 hours, and filtering the obtained reactant to obtain 0g of black powder; the check recovery rate was 0%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for recovering rhodium in rhodium-containing waste liquid is characterized by comprising the following steps:
concentrating the rhodium-containing waste liquid to prepare a concentrated solution; the weight percentage of rhodium in the concentrated solution is not lower than 1%;
adding nitrite and hydrazine hydrate into the concentrated solution to react, and collecting solid;
the molar ratio of the nitrite to rhodium in the rhodium-containing waste liquid is 10: 1-1: 1;
the molar ratio of the hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 0.5: 1-10: 1;
the reaction is carried out for 2-12 h at the temperature of 60-120 ℃;
the rhodium-containing waste liquid is waste liquid for preparing a rhodium-containing homogeneous catalyst, and the homogeneous catalyst is triphenylphosphine rhodium chloride or acetylacetonatocarbonylrhodium.
2. The method according to claim 1, wherein the molar ratio of the nitrite to the rhodium in the rhodium-containing waste liquid is 4: 1-2: 1.
3. the method according to claim 2, wherein the molar ratio of the nitrite to the rhodium in the rhodium-containing waste liquid is 29: 9.6 or 1.45: 0.55.
4. the method according to claim 1, wherein the molar ratio of hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 3: 1-1: 1.
5. the method according to claim 4, wherein the molar ratio of hydrazine hydrate to rhodium in the rhodium-containing waste liquid is 23: 9.6 or 1.1: 0.55.
6. the method for recovering rhodium from the rhodium-containing waste liquid according to claim 1, wherein the reaction is carried out at 65-75 ℃ for 8-12 h.
7. The method for recovering rhodium from a rhodium-containing waste liquid according to any one of claims 1 to 6, wherein the weight percentage of rhodium in the concentrated liquid is controlled to be 1 to 10%.
8. The method for recovering rhodium from the rhodium-containing waste liquid according to any one of claims 1 to 6, wherein the rhodium sulfate is prepared by dissolving the solid in sulfuric acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403604A (en) * | 2001-08-27 | 2003-03-19 | 中国石油化工股份有限公司 | Method of recovering metal rhodium from waste olefine carbonylating catalyst liquid |
| CN102277499A (en) * | 2011-08-11 | 2011-12-14 | 杭州凯大催化金属材料有限公司 | Method for recovering rhodium from organic waste liquid produced in carbonyl synthesis reaction |
| CN102453806A (en) * | 2010-11-03 | 2012-05-16 | 中国石油化工股份有限公司 | Method for recovering rhodium from waste solution of carbonyl synthesis waste rhodium catalyst |
| CN105441681A (en) * | 2014-09-26 | 2016-03-30 | 中国石油化工股份有限公司 | Method for recovery of rhodium from waste liquid containing rhodium phosphine complex catalyst |
| CN110607448A (en) * | 2019-09-27 | 2019-12-24 | 西安凯立新材料股份有限公司 | Method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid |
-
2020
- 2020-09-25 CN CN202011024493.4A patent/CN112111659B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403604A (en) * | 2001-08-27 | 2003-03-19 | 中国石油化工股份有限公司 | Method of recovering metal rhodium from waste olefine carbonylating catalyst liquid |
| CN102453806A (en) * | 2010-11-03 | 2012-05-16 | 中国石油化工股份有限公司 | Method for recovering rhodium from waste solution of carbonyl synthesis waste rhodium catalyst |
| CN102277499A (en) * | 2011-08-11 | 2011-12-14 | 杭州凯大催化金属材料有限公司 | Method for recovering rhodium from organic waste liquid produced in carbonyl synthesis reaction |
| CN105441681A (en) * | 2014-09-26 | 2016-03-30 | 中国石油化工股份有限公司 | Method for recovery of rhodium from waste liquid containing rhodium phosphine complex catalyst |
| CN110607448A (en) * | 2019-09-27 | 2019-12-24 | 西安凯立新材料股份有限公司 | Method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid |
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