CN110760689A - Method for removing iron in precious metal rhodium recovery process - Google Patents
Method for removing iron in precious metal rhodium recovery process Download PDFInfo
- Publication number
- CN110760689A CN110760689A CN201910933352.5A CN201910933352A CN110760689A CN 110760689 A CN110760689 A CN 110760689A CN 201910933352 A CN201910933352 A CN 201910933352A CN 110760689 A CN110760689 A CN 110760689A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- chloride
- mixture
- recovery process
- chlororhodate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
-
- 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
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- 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
- C22B11/06—Chloridising
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for removing iron in a precious metal rhodium recovery process, which comprises the following steps: concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture; chlorinating the mixture to obtain a mixture of rhodium chloride and ferric chloride; adding chloride and hydrochloric acid solution into a mixture of rhodium chloride and ferric chloride, reacting, and evaporating to dryness to prepare a mixture of chlororhodate and ferric chloride; washing the mixture of chlororhodate and ferric chloride with a polar organic solvent to remove ferric chloride; the remaining chlororhodate is made into metal rhodium or rhodium chloride. After the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution is concentrated and burned, a solid rhodium and iron oxide mixture is obtained.
Description
Technical Field
The invention relates to a method for removing iron in a recovery process of noble metal rhodium, which is suitable for a purification process of a noble metal rhodium compound, is particularly suitable for removing iron ions in a recovery process of a waste acetylacetonatocarbonylrhodium catalyst, and has higher application value in the aspect of removing iron from the rhodium compound.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
At present, the industrial production of butanol and octanol generally adopts propylene hydroformylation to synthesize butyraldehyde and further synthesize the butanol and octanol. The triphenylphosphine acetylacetonatocarbonylrhodium catalyst is the core of the production process. The catalyst contains noble metal rhodium, so that the noble metal rhodium has high value in recovery after the catalyst is out of service. However, in the using process of the catalyst, because of factors such as corrosion of equipment pipelines, entrainment of raw materials and the like, part of iron ions are inevitably carried in, so that the problem of recovery and purification of the noble metal rhodium is caused. At present, in China, a resin adsorption method is generally adopted in a rhodium compound iron removal process, but the resin has certain adsorption capacity on rhodium compounds, so that the recovery rate of noble metal rhodium is reduced, and meanwhile, the repeated adsorption and desorption process of the resin is complex, and a large amount of waste acid and waste water are also generated.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a method for removing iron in the recovery process of noble metal rhodium, which has the advantages of simple process, high recovery rate of noble metal rhodium, high purity and no generation of more waste acid and waste water.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for removing iron in a precious metal rhodium recovery process comprises the following steps:
concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture;
chlorinating the mixture to obtain a mixture of rhodium chloride and ferric chloride;
adding chloride and hydrochloric acid solution into a mixture of rhodium chloride and ferric chloride, reacting, and evaporating to dryness to prepare a mixture of chlororhodate and ferric chloride;
washing the mixture of chlororhodate and ferric chloride with a polar organic solvent to remove ferric chloride;
the remaining chlororhodate is made into metal rhodium or rhodium chloride.
After the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution is concentrated and burned, a solid rhodium and iron oxide mixture is obtained.
In some embodiments, the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution has a mass fraction after concentration of 0.5% to 1%.
In some embodiments, the mixture is chlorinated with chlorine gas at a temperature of 350-.
In some embodiments, the chloride salt is sodium chloride or potassium chloride.
Further, a mixture of rhodium chloride and ferric chloride is dissolved in a 0.8-1.2% hydrochloric acid solution, and sodium chloride is added according to the molar ratio of the rhodium chloride to the sodium chloride of 1: 5.5-6.5.
Further, the sodium chloride is of analytical grade. To avoid further entrainment of transition metal impurity ions.
In some embodiments, the polar organic solvent is absolute ethanol, acetone, or methanol. Washing with nonpolar organic solvent such as anhydrous ethanol and acetone, wherein ferric chloride is easily soluble in ethanol, and sodium chlororhodate is basically insoluble in ethanol. Ferric chloride carried by the washed absolute ethyl alcohol is dissolved in the ethyl alcohol, so that the separation of the ferric chloride and the chlororhodate is realized.
In some embodiments, the mixture of chlororhodate and ferric chloride is washed with the polar organic solvent at a temperature of from 30 to 50 ℃ (in this temperature interval, ferric chloride has high solubility in the solvent, and at too high a temperature, the solvent approaches the boiling point, resulting in substantial evaporation of the solvent), and the washing time is from 1 to 1.5 hours.
Further, the number of washing is 2 to 4. The ferric chloride can be removed more thoroughly by washing for many times, and the purity of the chlororhodate is improved.
In some embodiments, the method of making rhodium metal from chlororhodate is: hydrogen is adopted to reduce chlororhodanate to prepare metal rhodium, and the reaction temperature is 580-620 ℃.
In some embodiments, the method of making rhodium chloride from chlororhodate is: dissolving chlororhodate in deionized water, adding sodium hydroxide to prepare rhodium hydroxide, and adding hydrochloric acid to the rhodium hydroxide to prepare rhodium chloride.
The invention has the beneficial effects that:
the method has simple process, high recovery rate of the noble metal rhodium and high purity because the iron is washed and removed in the rhodium recovery process, and simultaneously, waste acid and waste water can not be generated.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1
Concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture; the mixture is chlorinated to obtain a mixture of rhodium chloride and ferric chloride. 20.9g of the chlorinated rhodium chloride mixture containing a certain amount of ferric chloride (also used as sample No. 0) was weighed out and dissolved in 100ml of a 1% hydrochloric acid solution having a mass concentration, 36.3g of sodium chloride was added thereto, and the mixture was sufficiently dissolved by stirring at 50 ℃. After insoluble matter was removed by suction filtration, the filtrate was decompressed to remove most of the liquid and dried in an oven at 110 ℃ to obtain a rose-red solid. The obtained solid was pulverized and transferred to 200ml of anhydrous ethanol, dissolved with stirring at 50 ℃ for 1 hour, and then filtered with suction. Obtaining a recovered sodium chlororhodate sample 1, grinding the sample 1 into powder again, adding 200ml of absolute ethyl alcohol, stirring and dissolving for 1h at the temperature of 50 ℃, and filtering. And (3) obtaining a recovered sodium chlororhodate sample 2, grinding the sample 2 into powder again, adding 200ml of absolute ethyl alcohol, stirring and dissolving for 1h at the temperature of 50 ℃, and filtering. And obtaining a recovered sodium chlororhodate sample 3, and quantitatively analyzing the iron ion contents of the sample 0, the sample 1, the sample 2 and the sample 3 by adopting an atomic absorption method, wherein the related data are shown in a table 1.
TABLE 1
| Serial number | Sample (I) | Sample size g | Iron ion content ppm |
| 1 | Sample 0, before iron removal | 0.5013 | 657 |
| 2 | Sample 1, iron removal once | 0.5007 | 132 |
| 3 | Sample 2, iron removal two times | 0.5011 | 67 |
| 4 | Sample 3, iron removal three times | 0.5017 | 29 |
Dissolving the dried sodium chlororhodate in 100ml of deionized water, slowly adding 100ml of NaOH solution with the mass concentration of 15% to generate precipitates, filtering to remove filtrate, and washing with the deionized water for 3-5 times. Adding 100ml of 1mol/L diluted hydrochloric acid to dissolve. Then the solution is evaporated to dryness to obtain rhodium chloride (the recovery rate of rhodium is 98.5-99%).
Example 2
20.9g of the rhodium chloride mixture prepared in example 1 and containing a certain amount of ferric chloride were weighed out and dissolved in 100ml of a 1% hydrochloric acid solution by mass, 36.3g of sodium chloride was added thereto, and the mixture was sufficiently dissolved by stirring at 50 ℃. After insoluble matter was removed by suction filtration, the filtrate was decompressed to remove most of the liquid and dried in an oven at 110 ℃ to obtain a rose-red solid. The obtained solid was pulverized and transferred to 200ml of anhydrous ethanol, dissolved with stirring at 50 ℃ for 1 hour, and then filtered with suction. And transferring the dried sodium chlororhodate into a reducing furnace, replacing with nitrogen, heating to 600 ℃, introducing hydrogen for reduction for 30min to obtain simple substance rhodium, wherein the recovery rate of rhodium is 99.0-99.5%, and the purity is 99.92%.
Example 3
20.9g of the rhodium chloride mixture prepared in example 1 and containing a certain amount of ferric chloride were weighed out and dissolved in 100ml of a 1.2% hydrochloric acid solution, 37.3g of sodium chloride was added, and the mixture was sufficiently dissolved by stirring at 50 ℃. After insoluble matter was removed by suction filtration, the filtrate was decompressed to remove most of the liquid and dried in an oven at 110 ℃ to obtain a rose-red solid. Grinding the obtained solid into powder, transferring the powder into 200ml of absolute ethyl alcohol, stirring and dissolving for 1.5h at the temperature of 40 ℃, and then carrying out suction filtration; this washing step was repeated twice. And transferring the dried rhodium chlororhodanate into a reduction furnace, replacing with nitrogen, heating to 620 ℃, introducing hydrogen for reduction for 30min to obtain simple substance rhodium, wherein the recovery rate of rhodium is 98.7-99.3%, and the purity is 99.93%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for removing iron in the recovery process of noble metal rhodium is characterized by comprising the following steps: the method comprises the following steps:
concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture;
chlorinating the mixture to obtain a mixture of rhodium chloride and ferric chloride;
adding chloride and hydrochloric acid solution into a mixture of rhodium chloride and ferric chloride, reacting, and evaporating to dryness to prepare a mixture of chlororhodate and ferric chloride;
washing the mixture of chlororhodate and ferric chloride with a polar organic solvent to remove ferric chloride;
the remaining chlororhodate is made into metal rhodium or rhodium chloride.
After the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution is concentrated and burned, a solid rhodium and iron oxide mixture is obtained.
2. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the mass fraction of the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution after concentration is 0.5-1%.
3. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the mixture was chlorinated with chlorine at a temperature of 350-.
4. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the chlorine salt is sodium chloride or potassium chloride.
5. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: dissolving a mixture of rhodium chloride and ferric chloride in a 0.8-1.2% hydrochloric acid solution, and adding sodium chloride according to the molar ratio of the rhodium chloride to the sodium chloride of 1: 5.5-6.5.
6. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the sodium chloride is of analytical grade.
7. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the polar organic solvent is absolute ethyl alcohol, acetone or methanol.
8. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: washing the mixture of chlororhodate and ferric chloride with a polar organic solvent at 30-50 deg.C for 1-1.5 h;
further, the number of washing is 2 to 4.
9. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the method for preparing metal rhodium by chlororhodate comprises the following steps: hydrogen is adopted to reduce chlororhodanate to prepare metal rhodium, and the reaction temperature is 580-620 ℃.
10. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the method for preparing rhodium chloride from chlororhodate comprises the following steps: dissolving chlororhodate in deionized water, adding sodium hydroxide to prepare rhodium hydroxide, and adding hydrochloric acid to the rhodium hydroxide to prepare rhodium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910933352.5A CN110760689B (en) | 2019-09-29 | 2019-09-29 | Method for removing iron in precious metal rhodium recovery process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910933352.5A CN110760689B (en) | 2019-09-29 | 2019-09-29 | Method for removing iron in precious metal rhodium recovery process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110760689A true CN110760689A (en) | 2020-02-07 |
| CN110760689B CN110760689B (en) | 2021-08-31 |
Family
ID=69330871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910933352.5A Active CN110760689B (en) | 2019-09-29 | 2019-09-29 | Method for removing iron in precious metal rhodium recovery process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110760689B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410242A (en) * | 2020-03-12 | 2020-07-14 | 鲁西催化剂有限公司 | Method for recovering rhodium chloride from rhodium slag |
| CN116692911A (en) * | 2023-08-07 | 2023-09-05 | 赣州市力道新能源有限公司 | Process for reducing magnetic substances in battery-grade lithium carbonate |
Citations (6)
| 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 |
| CN1414125A (en) * | 2001-10-26 | 2003-04-30 | 中国石油天然气股份有限公司 | Method of recovering rhodium from spent rhodium catalyst in carbongl group synthesis reaction |
| CN101177306A (en) * | 2007-11-12 | 2008-05-14 | 中国海洋石油总公司 | Method for recovering rhodium chloride from waste rhodium catalyst |
| CN105944768A (en) * | 2016-05-10 | 2016-09-21 | 能特科技有限公司 | Method for recovering rhodium catalyst from rhodium-containing wastewater |
| CN106319202A (en) * | 2016-11-14 | 2017-01-11 | 中海油天津化工研究设计院有限公司 | Method for preparing rhodium chloride hydrate from oxo synthesis waste rhodium catalyst |
| CN109554553A (en) * | 2018-12-17 | 2019-04-02 | 浙江省冶金研究院有限公司 | The recovery method of rhodium in a kind of spent rhodium catalyst |
-
2019
- 2019-09-29 CN CN201910933352.5A patent/CN110760689B/en active Active
Patent Citations (6)
| 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 |
| CN1414125A (en) * | 2001-10-26 | 2003-04-30 | 中国石油天然气股份有限公司 | Method of recovering rhodium from spent rhodium catalyst in carbongl group synthesis reaction |
| CN101177306A (en) * | 2007-11-12 | 2008-05-14 | 中国海洋石油总公司 | Method for recovering rhodium chloride from waste rhodium catalyst |
| CN105944768A (en) * | 2016-05-10 | 2016-09-21 | 能特科技有限公司 | Method for recovering rhodium catalyst from rhodium-containing wastewater |
| CN106319202A (en) * | 2016-11-14 | 2017-01-11 | 中海油天津化工研究设计院有限公司 | Method for preparing rhodium chloride hydrate from oxo synthesis waste rhodium catalyst |
| CN109554553A (en) * | 2018-12-17 | 2019-04-02 | 浙江省冶金研究院有限公司 | The recovery method of rhodium in a kind of spent rhodium catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 李子东，李广宇，于敏编著: "《实用胶粘剂原材料手册》", 31 July 1999, 国防工业出版社 * |
| 陈寿椿编: "《重要无机化学反应》", 31 December 1982, 上海科学技术出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410242A (en) * | 2020-03-12 | 2020-07-14 | 鲁西催化剂有限公司 | Method for recovering rhodium chloride from rhodium slag |
| CN111410242B (en) * | 2020-03-12 | 2021-07-02 | 鲁西催化剂有限公司 | Method for recovering rhodium chloride from rhodium slag |
| CN116692911A (en) * | 2023-08-07 | 2023-09-05 | 赣州市力道新能源有限公司 | Process for reducing magnetic substances in battery-grade lithium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110760689B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103160690B (en) | Method for recovering metal oxide from SCR denitration waste catalyst | |
| CN110760689B (en) | Method for removing iron in precious metal rhodium recovery process | |
| CN103805794B (en) | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash | |
| KR20160101003A (en) | Method for recovering ash from waste incineration | |
| CN105349803A (en) | Method for separating tungsten and molybdenum from molybdenum-contained phosphotungstic acid/phosphowolframate solution | |
| US4169130A (en) | Liquid/liquid extraction of gallium values from highly basic aqueous solutions thereof | |
| JP5032400B2 (en) | Nickel oxide | |
| CN110627761A (en) | Method for synthesizing myricetin | |
| CN102701263A (en) | Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation | |
| CN109336177B (en) | Method for cleanly producing high-purity vanadium pentoxide by using hydrogen peroxide and ammonia water | |
| CN114349079A (en) | Recycling treatment method for nickel slag solid waste in nitrogen trifluoride gas electrolysis production | |
| CN112813287B (en) | Method for recovering molybdenum from waste hydrogenation catalyst | |
| CN113621834A (en) | Method for selectively dephosphorizing molybdenum and phosphorus mixed solution | |
| CN104060095A (en) | Method of recovering palladium from palladium-loading aluminum oxide waste catalyst | |
| JP2014118598A (en) | Method for separating rare earth element | |
| CN109110828B (en) | Method for efficiently preparing solid ruthenium nitrosyl nitrate | |
| CN115353126B (en) | Method for separating valuable metal elements based on imidazole ionic liquid | |
| CN114807616B (en) | Method for recovering enriched palladium from palladium-containing organic waste liquid | |
| CN114934169B (en) | Method for recycling tungsten-containing waste | |
| CN108912328A (en) | A kind of preparation method of heavy metal ion chelating agent | |
| CN101768045B (en) | Method for preparing halogenated hydrocarbons from strong acidic ionic liquid | |
| CN116411183A (en) | Comprehensive smelting method of low-grade molybdenum concentrate containing tungsten | |
| CN111893326A (en) | Method for extracting tungsten by two-step acid decomposition method | |
| CN113717129A (en) | Synthetic method of piperazine-N, N-bisdithiocarbamate serving as solid chelating agent | |
| CN108821354B (en) | Method for preparing iridium nitrate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |