CN111254289A - 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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- CN111254289A CN111254289A CN202010252830.9A CN202010252830A CN111254289A CN 111254289 A CN111254289 A CN 111254289A CN 202010252830 A CN202010252830 A CN 202010252830A CN 111254289 A CN111254289 A CN 111254289A
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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
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- 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
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Abstract
The invention relates to a method for recovering rhodium from rhodium-containing organic waste liquid, which destroys macromolecular organic matters in a rhodium-containing waste organic solvent into micromolecules, and removes the micromolecules by using a concentration method, thereby greatly reducing the amount of rhodium-containing waste materials to be incinerated, and reducing the rhodium loss caused by flue gas entrainment in the incineration process while reducing the incineration amount; and then the programmed temperature rise ashing is used, the rhodium loss caused by flue gas entrainment is reduced to a certain extent, and finally the noble metal rhodium in the rhodium-containing waste liquid is recovered in a high yield by two pipes. The yield of rhodium in the invention reaches more than 99%.
Description
Technical Field
The invention relates to a method for recovering rhodium from a waste organic solvent containing rhodium, and relates to the fields of precious metal extraction, chemical experimental method research, chemical technology and environmental protection.
Background
Rhodium in platinum group metals has unique physical and chemical characteristics, particularly high catalytic activity and high selectivity, so that the rhodium is widely applied to the aspects of petroleum industry catalysts, automobile three-way tail gas purifiers, catalytic hydrogenation, methanol carbonylation, olefin hydroformylation and the like, and the market demand is large. But the rhodium has little content in the earth crust, is difficult to separate and purify and belongs to a scarce resource; however, the rhodium mineral resources in China are deficient, the secondary recovery and reutilization technology is not mature, import is mainly used, the possibility of obtaining the resources of domestic production enterprises is greatly limited, and the development of the domestic catalyst production enterprises is severely restricted. If the recycling economy is vigorously developed, the rhodium metal is efficiently purified and recycled from the waste, so that the method has important significance for enlarging the rhodium metal resource scale, improving the self-supply guarantee of the rhodium metal to meet the high growth demand of the market, and in the fields of economic development, scientific research, environmental protection and the like.
At present, the method for recovering rhodium from rhodium-containing organic waste liquid is mainly divided into a pyrogenic method and a wet method, the two methods have the defects respectively, the yield and the purity of wet recovery are not high, and the flue gas entrainment in the pyrogenic incineration process causes rhodium loss. Therefore, the invention focuses on the effective improvement of the yield and efficiency of the noble metal rhodium by determining a suitable recovery method according to the characteristics of the rhodium-containing organic waste liquid and creating a new rhodium recovery method.
Disclosure of Invention
The invention aims to provide a method for effectively improving the yield and efficiency of rhodium recovery from rhodium-containing organic waste liquid. The method can effectively destroy macromolecular organic matters in the rhodium-containing waste organic solvent into micromolecules, and remove the micromolecules by using a concentration method, thereby greatly reducing the amount of rhodium-containing waste materials to be incinerated, and reducing the rhodium loss caused by flue gas entrainment in the incineration process while reducing the incineration amount; and then the programmed temperature rise ashing is used, the rhodium loss caused by flue gas entrainment is reduced to a certain extent, and finally the noble metal rhodium in the rhodium-containing waste liquid is recovered in a high yield by two pipes.
The specific technical scheme of the invention is as follows:
a method for recovering rhodium from rhodium-containing waste organic solvent comprises the following steps:
(1) adding a waste organic solvent containing rhodium into an intermittent reaction kettle, simultaneously adding a copper ion catalyst and alkali, oxygenating, increasing the pressure, and heating to perform wet oxidation reaction to obtain wet oxidation reaction liquid;
(2) concentrating the wet oxidation reaction liquid under reduced pressure until no liquid is evaporated out to obtain a rhodium-containing concentrated liquid;
(3) and (3) carrying out temperature programming ashing on the rhodium-containing concentrated solution, and carrying out acid washing after ashing to obtain rhodium ash.
Further, the copper ion catalyst can be one or more of copper sulfate, copper nitrate and copper chloride; the base may be sodium hydroxide and/or potassium hydroxide.
The pressure range is 1.5-5MPa, the temperature is increased along with the increase of the pressure, and the pressure range of 1.5-5MPa corresponds to the temperature range of 200-260 ℃.
The temperature programming ashing process comprises the following steps: keeping at 200 deg.C for 1h, heating to 250 deg.C for 1h, heating to 300 deg.C for 1h, heating to 350 deg.C for 2h, heating to 400 deg.C for 2h, and heating to 600 deg.C for 4 h.
The yield of rhodium in the invention reaches more than 99%.
The invention has the following advantages:
(1) the wet oxidation method is applied to the rhodium recovery process and organically combined with temperature programmed ashing, the wet oxidation method oxidizes and destroys macromolecular organic matters into micromolecules, then the micromolecular organic matters are removed through reduced pressure concentration, the treatment amount in the incineration process is greatly reduced, the rhodium loss in the recovery process is effectively reduced through the combination of the wet oxidation method and the temperature programmed ashing, and the rhodium yield reaches 99.5%.
(2) The method can effectively destroy macromolecular organic matters in the rhodium-containing waste liquid into micromolecular organic matters, can reduce the mass of the rhodium-containing organic waste liquid by more than 90 percent through wet oxidation, and has the advantages of small environmental pollution and high rhodium yield.
Detailed Description
The present invention will be further illustrated below with reference to specific examples and comparative examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the embodiments of the present invention, and these equivalents also fall within the scope of the claims appended hereto.
Example 1
The rhodium content in the rhodium-containing organic waste liquid raw material used in the experiment is 0.1 percent, the copper ion catalyst is copper sulfate, and the alkali is sodium hydroxide.
Adding 200.0g of rhodium-containing organic waste liquid raw material into a reaction kettle, wherein the addition of copper ions is 300mg/L, the addition of alkali is 20g/L, oxygenating to increase the pressure to 3Mpa, controlling the reaction temperature at 240 ℃, carrying out wet oxidation reaction for 30h, reducing the temperature and relieving the pressure to obtain wet oxidation reaction liquid, carrying out reduced pressure concentration on the wet oxidation reaction liquid until no liquid is evaporated out to obtain 20g of rhodium-containing concentrated liquid, and carrying out temperature programmed ashing on the rhodium-containing concentrated liquid, wherein the temperature programmed flow is as follows: keeping the temperature at 200 ℃ for 1h, raising the temperature to 250 ℃ for 1h, raising the temperature to 300 ℃ for 1h, raising the temperature to 350 ℃ for 2h, raising the temperature to 400 ℃ for 2h, raising the temperature to 600 ℃ for 4h, washing and drying an ashing product by using 10g of concentrated hydrochloric acid to obtain 2g of rhodium ash, and detecting that the rhodium content of the rhodium ash is 9.95 percent and the rhodium yield is 99.5 percent.
Comparative example 1
The rhodium content in the rhodium-containing organic waste liquid raw material used in the experiment is 0.1 percent, the copper ion catalyst is copper sulfate, and the alkali is sodium hydroxide.
Adding 200.0g of rhodium-containing organic waste liquid raw material into a reaction kettle, wherein the adding amount of copper ions is 300mg/L, the adding amount of alkali is 20g/L, oxygenating to increase the pressure to 3Mpa, controlling the reaction temperature at 240 ℃, carrying out wet oxidation reaction for 30h, cooling and relieving pressure to obtain wet oxidation reaction liquid, carrying out reduced pressure concentration on the wet oxidation reaction liquid until no liquid is evaporated out to obtain 20g of rhodium-containing concentrated liquid, raising the temperature of the rhodium-containing concentrated liquid to 600 ℃, ashing for 4h, pickling and drying ashing products by using 10g of concentrated hydrochloric acid to obtain 1.95g of rhodium ash, detecting the content of rhodium in the rhodium ash to be 9.74%, and obtaining the yield of rhodium by 95%.
Example 2
The rhodium content in the rhodium-containing organic waste liquid raw material used in the experiment is 0.1 percent, the copper ion catalyst is copper sulfate, and the alkali is sodium hydroxide.
Adding 200.0g of rhodium-containing organic waste liquid raw material into a reaction kettle, wherein the addition of copper ions is 300mg/L, the addition of alkali is 18g/L, oxygenating to increase the pressure to 2Mpa, controlling the reaction temperature at 220 ℃, carrying out wet oxidation reaction for 20h, reducing the temperature and relieving the pressure to obtain wet oxidation reaction liquid, carrying out reduced pressure concentration on the wet oxidation reaction liquid until no liquid is evaporated out to obtain 30g of rhodium-containing concentrated liquid, and carrying out temperature programmed ashing on the rhodium-containing concentrated liquid, wherein the temperature programmed flow is as follows: keeping at 200 ℃ for 1h, raising the temperature to 250 ℃ for 1h, raising the temperature to 300 ℃ for 1h, raising the temperature to 350 ℃ for 2h, raising the temperature to 400 ℃ for 2h, raising the temperature to 600 ℃ for 4h, washing and drying an ashing product by using 10g of concentrated hydrochloric acid to obtain 3g of rhodium ash, and detecting that the rhodium content of the rhodium ash is 6.60% and the rhodium yield is 99%.
Comparative example 2
200.0g of rhodium-containing organic waste liquid raw material is taken for temperature programming ashing, and the temperature programming flow is as follows: keeping at 200 ℃ for 1h, raising the temperature to 250 ℃ for 1h, raising the temperature to 300 ℃ for 1h, raising the temperature to 350 ℃ for 2h, raising the temperature to 400 ℃ for 2h, raising the temperature to 600 ℃ for 4h, washing and drying an ashing product by using 10g of concentrated hydrochloric acid to obtain 20g of rhodium ash, and detecting that the rhodium content of the rhodium ash is 0.96 percent and the rhodium yield is 96 percent.
Example 3
The rhodium content in the rhodium-containing organic waste liquid raw material used in the experiment is 0.1 percent, the copper ion catalyst is copper sulfate, and the alkali is sodium hydroxide.
Adding 200.0g of rhodium-containing organic waste liquid raw material into a reaction kettle, wherein the addition of copper ions is 300mg/L, the addition of alkali is 20g/L, oxygenating to increase the pressure to 3Mpa, controlling the reaction temperature at 240 ℃, carrying out wet oxidation reaction for 30h, reducing the temperature and relieving the pressure to obtain wet oxidation reaction liquid, carrying out reduced pressure concentration on the wet oxidation reaction liquid until no liquid is evaporated out to obtain 20g of rhodium-containing concentrated liquid, and carrying out temperature programmed ashing on the rhodium-containing concentrated liquid, wherein the temperature programmed flow is as follows: keeping the temperature at 200 ℃ for 1h, raising the temperature to 250 ℃ for 1h, raising the temperature to 300 ℃ for 1h, raising the temperature to 350 ℃ for 2h, raising the temperature to 400 ℃ for 2h, raising the temperature to 600 ℃ for 4h, washing and drying an ashing product by using 10g of concentrated hydrochloric acid to obtain 2g of rhodium ash, and detecting that the rhodium content of the rhodium ash is 9.95 percent and the rhodium yield is 99.5 percent.
Comparative example 3
The rhodium content in the rhodium-containing organic waste liquid raw material used in the experiment is 0.1 percent, the copper ion catalyst is copper sulfate, and the alkali is sodium hydroxide.
Adding 200.0g of rhodium-containing organic waste liquid raw material into a reaction kettle, wherein the addition of copper ions is 300mg/L, the addition of alkali is 20g/L, oxygenating to increase the pressure to 3Mpa, controlling the reaction temperature at 240 ℃, carrying out wet oxidation reaction for 30h, reducing the temperature and relieving the pressure to obtain wet oxidation reaction liquid, carrying out reduced pressure concentration on the wet oxidation reaction liquid until no liquid is evaporated out to obtain 20g of rhodium-containing concentrated liquid, and carrying out temperature programmed ashing on the rhodium-containing concentrated liquid, wherein the temperature programmed flow is as follows: keeping at 200 ℃ for 1h, raising the temperature to 250 ℃ for 1h, raising the temperature to 300 ℃ for 1h, raising the temperature to 600 ℃ for 4h, washing and drying the ashing product by using 10g of concentrated hydrochloric acid to obtain 1.95g of rhodium ash, detecting that the rhodium content of the rhodium ash is 10.05 percent, and the rhodium yield is 98 percent.
Claims (6)
1. A method for recovering rhodium from rhodium-containing waste organic solvent comprises the following steps:
(1) adding a waste organic solvent containing rhodium into an intermittent reaction kettle, simultaneously adding a copper ion catalyst and alkali, oxygenating, increasing the pressure, and heating to perform wet oxidation reaction to obtain wet oxidation reaction liquid;
(2) concentrating the wet oxidation reaction liquid under reduced pressure until no liquid is evaporated out to obtain a rhodium-containing concentrated liquid;
(3) and (3) carrying out temperature programming ashing on the rhodium-containing concentrated solution, and carrying out acid washing after ashing to obtain rhodium ash.
2. The method of claim 1, wherein the copper ion catalyst is one or more of copper sulfate, copper nitrate, and copper chloride.
3. The method according to claim 1, wherein the base is sodium hydroxide and/or potassium hydroxide.
4. The method of claim 1, wherein said oxygenating increases pressure in the pressure range of 1.5-5 MPa.
5. The method according to claim 1, wherein the reaction temperature of the wet oxidation reaction increases with increasing pressure, with a pressure range of 1.5-5MPa corresponding to a temperature range of 200-260 ℃.
6. The method of claim 1, wherein the temperature programmed ashing process is as follows: keeping at 200 deg.C for 1h, heating to 250 deg.C for 1h, heating to 300 deg.C for 1h, heating to 350 deg.C for 2h, heating to 400 deg.C for 2h, and heating to 600 deg.C for 4 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010252830.9A CN111254289A (en) | 2020-04-01 | 2020-04-01 | Method for recovering rhodium from rhodium-containing waste liquid |
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| CN202010252830.9A CN111254289A (en) | 2020-04-01 | 2020-04-01 | Method for recovering rhodium from rhodium-containing waste liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113528827A (en) * | 2021-06-30 | 2021-10-22 | 济南恒誉环保科技股份有限公司 | Method for separating precious metals from waste liquid phase organic matter by adopting thermal cracking |
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2020
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113528827A (en) * | 2021-06-30 | 2021-10-22 | 济南恒誉环保科技股份有限公司 | Method for separating precious metals from waste liquid phase organic matter by adopting thermal cracking |
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Address after: 262725 Shandong city of Weifang province Shouguang Hou town project area nine west 500 meters north of the new road Applicant after: Shandong Boyuan Pharmaceutical Chemical Co., Ltd Address before: 262725 Shandong city of Weifang province Shouguang Hou town project area nine west 500 meters north of the new road Applicant before: SHANDONG BOYUAN PHARMACEUTICAL & CHEMICAL Co.,Ltd. |
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