CN112320999A - Method for recovering rhodium in rhodium-containing wastewater - Google Patents
Method for recovering rhodium in rhodium-containing wastewater Download PDFInfo
- Publication number
- CN112320999A CN112320999A CN202011011473.3A CN202011011473A CN112320999A CN 112320999 A CN112320999 A CN 112320999A CN 202011011473 A CN202011011473 A CN 202011011473A CN 112320999 A CN112320999 A CN 112320999A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- containing wastewater
- recovering
- sulfide
- nitrite
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for recovering rhodium in rhodium-containing wastewater, which comprises the following steps: adjusting the pH value of the rhodium-containing wastewater to be more than 7, and then adding nitrite and sulfide to react to prepare a first reactant; adding an alcohol compound into the first reactant for reaction, and collecting a solid. The recovery method can effectively recover rhodium in the rhodium-containing wastewater with low concentration, and has high recovery rate and high product purity.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for recovering rhodium in rhodium-containing wastewater.
Background
Among the platinum group metals, metal rhodium is increasingly used in the field of organic synthesis due to its low specific electrochemical properties and excellent catalytic properties. Rhodium can receive special spatial structures formed by a plurality of different complexes, and therefore can be applied to the field of chemical catalysis.
Homogeneous rhodium catalysts are generally insoluble in water, so the amount of metallic rhodium contained in the waste water produced during the use of rhodium catalysts is very small, but a relatively large amount of organic solvent is required for the catalysis. To overcome this problem, the rhodium catalysts are currently rendered well water-soluble by sulfonation, thereby reducing the use of organic solvents in the production process, but with the consequent relatively large increase in rhodium content in the resulting wastewater. The large amount of rhodium loss is a main reason for restricting the large-scale application of the water-soluble rhodium catalyst in the using process.
Although the amount of rhodium in the waste water is greatly increased compared with that before sulfonation, the content of rhodium in the waste water is still low in general, especially when the water consumption in the production process is high, so that the recovery of rhodium in the waste water with low concentration of rhodium is difficult. In the prior art, rhodium is extracted and recovered by a direct complexing precipitation mode, but the recovery rate and the purity are difficult to guarantee.
Disclosure of Invention
Based on this, it is necessary to provide a method for recovering rhodium from rhodium-containing wastewater. The recovery method can effectively recover rhodium in the rhodium-containing wastewater with low concentration, and has high recovery rate and high product purity.
The specific technical scheme is as follows:
a method for recovering rhodium in rhodium-containing wastewater comprises the following steps:
adjusting the pH value of the rhodium-containing wastewater to be more than 7, and then adding nitrite and sulfide to react to prepare a first reactant;
adding an alcohol compound into the first reactant for reaction, and collecting a solid.
In one embodiment, the oxidative complexation reaction is carried out at 50-100 ℃ for 8-12 hours.
In one embodiment, the nitrite salt is sodium nitrite.
In one embodiment, the sulfide is sodium sulfide.
In one embodiment, the molar ratio of the nitrite, sulfide, and rhodium in the rhodium-containing wastewater is 1: 1: 1-5: 5: 1.
in one embodiment, the reduction reaction is carried out at 30-50 ℃ for 1-3 h.
In one embodiment, the alcohol compound is methanol or ethanol.
In one embodiment, the molar ratio of the alcohol compound to rhodium in the rhodium-containing wastewater is 5: 1-15: 1.
in one embodiment, the solid is dissolved in sulfuric acid to produce a rhodium sulfate solution.
In one embodiment, the concentration of rhodium in the rhodium-containing wastewater is 1-1000 ppm.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for recovering rhodium in rhodium-containing wastewater, which is characterized in that nitrite and sulfide are added into the rhodium-containing wastewater after pH adjustment, wherein the nitrite can oxidize rhodium in the wastewater from low valence to 3 valence, and the 3-valence rhodium can be complexed with the sulfide to form a compound similar to rhodium sulfide. On the basis, alcohol compounds are added to reduce the rhodium sulfide compounds to promote complete precipitation and reduce the rhodium sulfide compounds into sponge rhodium. By combining the steps, the rhodium can be recovered from the rhodium-containing wastewater with high recovery rate, and the method is particularly suitable for recovering rhodium from the rhodium-containing wastewater with low concentration (such as 1-1000 ppm) and has high product purity.
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 wastewater, which comprises the following steps:
adjusting the pH value of the rhodium-containing wastewater to be more than 7, and then adding nitrite and sulfide to carry out oxidation complex reaction to prepare a first reactant;
and adding an alcohol compound into the first reactant to perform a reduction reaction, and collecting a solid.
The process of the recovery method is expressed by the following chemical equation:
Rhn++NO2 -+S2-→Rh2S3+N2
Rh2S3+CH3OH→Rh+CH2O+S2-
it is understood that the rhodium-containing waste water refers to waste water containing rhodium ions, complexes of rhodium, or other rhodium in an optional form. In one specific embodiment, the rhodium-containing wastewater is wastewater containing a water-soluble rhodium complex homogeneous catalyst. More specifically, the rhodium-containing wastewater is a deactivated sulfonated or carboxylated rhodium coordination homogeneous catalyst, such as a homogeneous catalyst of TPPTS complex.
Further, the recovery method is suitable for recovering rhodium in the low-concentration rhodium-containing wastewater, and specifically, the concentration of rhodium in the rhodium-containing wastewater is 1-1000 ppm.
In one specific embodiment, the oxidative complexation reaction is carried out at 50-100 ℃ for 8-12 hours. The reaction conditions of the oxidation and complexation are reasonably controlled, so that the oxidation reaction and the complexation reaction can be completed by a one-pot method, the working procedures are simplified, the production efficiency is improved, meanwhile, the reaction conversion rate is ensured, and the recovery rate is improved. Preferably, the oxidative complexation reaction is carried out at 65-75 ℃ for 8-12 hours.
In one specific embodiment, the nitrite is sodium nitrite.
In one particular embodiment, the sulfide is sodium sulfide.
In one specific embodiment, the molar ratio of the nitrite, sulfide and rhodium in the rhodium-containing wastewater is 1: 1: 1-5: 5: 1. the molar ratio of the nitrite to the sulfide to the rhodium in the rhodium-containing wastewater is reasonably regulated, so that the low-valence rhodium can be completely oxidized into the 3-valence rhodium, and the 2-valence rhodium is subjected to complex precipitation as much as possible.
In one specific embodiment, the reduction reaction is carried out at 30-50 ℃ for 1-3 h. Because the types of ligands in the rhodium-containing wastewater are generally more, and the complex precipitation is difficult to completely complex only by virtue of the complexation of sulfides, the reduction of alcohol compounds is required to be further precipitated, and the conditions of the reduction reaction are reasonably regulated and controlled in the process so as to promote the precipitation to be completely separated out in the form of sponge rhodium. Preferably, the reduction reaction is carried out for 1-3 h at 30-35 ℃.
In one specific embodiment, the alcohol compound is methanol or ethanol.
In one specific embodiment, the molar ratio of the alcohol compound to rhodium in the rhodium-containing wastewater is 5: 1-15: 1.
in one specific example, the adjusting agent used to adjust the pH of the rhodium-containing wastewater to greater than 7 can be hydrochloric acid and/or sodium hydroxide.
Further, in one specific example, the solid is dissolved with sulfuric acid to prepare a rhodium sulfate solution.
In one specific embodiment, the molar ratio of the sulfuric acid to rhodium in the rhodium-containing wastewater is 15: 1-40: 1.
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 wastewater, comprising the following steps:
(1) obtaining 1000 liters of TPPTS acetylacetonatocarbonylrhodium waste liquid with low concentration (rhodium concentration is 1000ppm) (wherein, the molar weight of rhodium is calculated to be 9.6mol), and adjusting the pH value of the rhodium-containing waste water to 9 by hydrochloric acid and sodium hydroxide;
(2) adding 2kg of sodium nitrite (29mol) and 6.96kg of sodium sulfide nonahydrate (29mol) into the rhodium-containing wastewater subjected to pH adjustment in the step (1), heating to 70 ℃, and stirring for 10 hours;
(3) adding 3L of methanol (74.1mol) into the reaction product obtained in the step (3), stirring for 2 hours at 30 ℃, filtering, and collecting solid to obtain 992 g of black powder;
(4) adding 10L (186mol) of concentrated sulfuric acid into the black powder obtained in the step (3) to obtain a rhodium sulfate solution; the calculated rhodium recovery was 99.2%.
Example 2
The embodiment is a method for recovering rhodium in rhodium-containing wastewater, comprising the following steps:
(1) obtaining 1000 liters of TPPTS acetylacetonatocarbonylrhodium waste liquid with low concentration (rhodium concentration is 5ppm) (wherein, the molar weight of rhodium is calculated to be 0.05mol), and adjusting the pH value of the rhodium-containing waste water to be more than 9 by hydrochloric acid and sodium hydroxide;
(2) adding 10g of sodium nitrite (0.145mol) and 24g of sodium sulfide nonahydrate (0.1mol) into the rhodium-containing wastewater subjected to pH adjustment in the step (1), heating to 70 ℃, and stirring for 10 hours;
(3) adding 30mL of methanol (0.74mol) into the reaction product obtained in the step (3), stirring at 30 ℃ for 2 hours, filtering, and collecting a solid to obtain 4.8 g of black powder;
(4) adding 0.1L (1.8mol) of concentrated sulfuric acid into the black powder obtained in the step (3) to obtain a rhodium sulfate solution; the calculated rhodium recovery was 96%.
Comparative example 1
The comparative example is a method for recovering rhodium from rhodium-containing wastewater, and the steps are the same as those of example 1, except that: the step (3) of carrying out the reduction reaction with an alcohol compound is not carried out.
The method comprises the following specific steps:
(1) obtaining 1000 liters of rhodium-containing wastewater with low concentration (the concentration of rhodium is 1000ppm), and adjusting the pH value of the rhodium-containing wastewater to be more than 7 by using hydrochloric acid and sodium hydroxide;
(2) adding 2kg of sodium nitrite (29mol) and 6.96kg of sodium sulfide nonahydrate (29mol) into the rhodium-containing wastewater subjected to pH adjustment in the step (1), heating to 70 ℃, and stirring for 10 hours; filtering, collecting solid to obtain 0g of black powder; the calculated rhodium recovery was 0%.
Comparative example 2
The comparative example is a method for recovering rhodium from rhodium-containing wastewater, and the steps are the same as those of example 1, except that: in the step (2), only sodium sulfide is added for reaction.
The method comprises the following specific steps:
(1) obtaining 1000 liters of rhodium-containing wastewater with low concentration (the concentration of rhodium is 1000ppm), and adjusting the pH value of the rhodium-containing wastewater to be more than 7 by using hydrochloric acid and sodium hydroxide;
(2) adding 6.96kg of sodium sulfide nonahydrate (29mol) into the rhodium-containing wastewater subjected to pH adjustment in the step (1), heating to 70 ℃, and stirring for 10 hours;
(3) adding 3L of methanol (74.1mol) into the reaction product obtained in the step (3), stirring for 2 hours at 30 ℃, filtering, and collecting solid to obtain 497 g of black powder;
(4) adding 10L (182mol) of concentrated sulfuric acid into the black powder obtained in the step (3) to obtain a rhodium sulfate solution; the calculated rhodium recovery was 50%.
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 (10)
1. A method for recovering rhodium in rhodium-containing wastewater is characterized by comprising the following steps:
adjusting the pH value of the rhodium-containing wastewater to be more than 7, and then adding nitrite and sulfide to react to prepare a first reactant;
adding an alcohol compound into the first reactant for reaction, and collecting a solid.
2. The method for recovering rhodium from rhodium-containing wastewater according to claim 1, wherein the oxidation-complexation reaction is carried out at 50-100 ℃ for 8-12 hours.
3. The method for recovering rhodium from rhodium-containing wastewater according to claim 1, wherein the nitrite is sodium nitrite.
4. The method for recovering rhodium from rhodium-containing wastewater according to claim 1, wherein the sulfide is sodium sulfide.
5. The method according to claim 1, wherein the molar ratio of the nitrite to the sulfide to the rhodium in the rhodium-containing wastewater is 1: 1: 1-5: 5: 1.
6. the method for recovering rhodium from rhodium-containing wastewater according to claim 1, wherein the reduction reaction is carried out at 30-50 ℃ for 1-3 h.
7. The method for recovering rhodium from rhodium-containing wastewater according to claim 1, wherein the alcohol compound is methanol or ethanol.
8. The method according to claim 1, wherein the molar ratio of the alcohol compound to rhodium in the rhodium-containing wastewater is 5: 1-15: 1.
9. the method for recovering rhodium from rhodium-containing wastewater according to any one of claims 1 to 8, wherein the solid is dissolved in sulfuric acid to prepare a rhodium sulfate solution.
10. The method for recovering rhodium from rhodium-containing wastewater according to any one of claims 1 to 8, wherein the concentration of rhodium in the rhodium-containing wastewater is 1 to 1000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011011473.3A CN112320999B (en) | 2020-09-23 | 2020-09-23 | Method for recovering rhodium in rhodium-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011011473.3A CN112320999B (en) | 2020-09-23 | 2020-09-23 | Method for recovering rhodium in rhodium-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112320999A true CN112320999A (en) | 2021-02-05 |
| CN112320999B CN112320999B (en) | 2022-07-15 |
Family
ID=74303649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011011473.3A Active CN112320999B (en) | 2020-09-23 | 2020-09-23 | Method for recovering rhodium in rhodium-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112320999B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166404A (en) * | 1959-03-04 | 1965-01-19 | Engelhard Ind Inc | Recovery of rhodium from fission products |
| JPS5665946A (en) * | 1979-11-01 | 1981-06-04 | Mitsubishi Chem Ind Ltd | Rhodium separating and recovering method |
| US5364445A (en) * | 1992-08-04 | 1994-11-15 | N.E. Chemcat Corporation | Recovery method of rhodium |
| CN102923796A (en) * | 2012-11-05 | 2013-02-13 | 中国海洋石油总公司 | Method for preparing rhodium chloride hydrate by recovering rhodium from dead rhodium catalyst of oxo synthesis |
| 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 |
| CN111996386A (en) * | 2020-08-28 | 2020-11-27 | 江苏北矿金属循环利用科技有限公司 | Method for recovering rhodium from rhodium-containing homogeneous phase waste catalyst |
-
2020
- 2020-09-23 CN CN202011011473.3A patent/CN112320999B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166404A (en) * | 1959-03-04 | 1965-01-19 | Engelhard Ind Inc | Recovery of rhodium from fission products |
| JPS5665946A (en) * | 1979-11-01 | 1981-06-04 | Mitsubishi Chem Ind Ltd | Rhodium separating and recovering method |
| US5364445A (en) * | 1992-08-04 | 1994-11-15 | N.E. Chemcat Corporation | Recovery method of rhodium |
| CN102923796A (en) * | 2012-11-05 | 2013-02-13 | 中国海洋石油总公司 | Method for preparing rhodium chloride hydrate by recovering rhodium from dead rhodium catalyst of oxo synthesis |
| 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 |
| CN111996386A (en) * | 2020-08-28 | 2020-11-27 | 江苏北矿金属循环利用科技有限公司 | Method for recovering rhodium from rhodium-containing homogeneous phase waste catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 裴洪营等: "从有机废料中回收铑的技术进展", 《贵金属》, no. 04 * |
| 赵家春等: "低浓度含铑有机废液中硫化沉铑工艺优化研究", 《贵金属》, 26 November 2018 (2018-11-26) * |
| 黄礼煌: "《贵金属提取新技术》", 30 November 2016 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112320999B (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0382720A (en) | Method for recovering indium | |
| KR20190079113A (en) | Catalyst and electrode and electro-fenton reaction system usingby | |
| JP2007270262A (en) | Method for collecting indium | |
| CN105152433A (en) | Method for removing COD (chemical oxygen demand) from copper/molybdenum extraction raffinate mixed wastewater | |
| CN112320999B (en) | Method for recovering rhodium in rhodium-containing wastewater | |
| JP4079018B2 (en) | Method for purifying cobalt aqueous solution | |
| JPH07115875B2 (en) | Vanadium regeneration method | |
| CN109970165B (en) | Heavy metal trapping agent and preparation method thereof | |
| JPH075511B2 (en) | Method for producing carboxylate | |
| CN113402379A (en) | Green production method of 1,1 '-binaphthyl-8, 8' -dicarboxylic acid | |
| EP3904329A1 (en) | Process for hydrodefluorination of aromatic trifluoromethyl derivatives | |
| CN112111659B (en) | Method for recovering rhodium from rhodium-containing waste liquid | |
| CN108821354B (en) | Method for preparing iridium nitrate solution | |
| JPH08225517A (en) | Manufacture of noble metal salt of nonoxidizing acid by direct reaction | |
| CN106008279A (en) | Method for preparing azodicarbonamide by oxygen oxidation | |
| CN108047276B (en) | Method for synthesizing ruthenium (III) acetylacetonate | |
| KR910004174B1 (en) | Process for producing 2-quinoxalinols | |
| JP2621185B2 (en) | Production of metal carbonates as catalyst precursors | |
| JPH01159056A (en) | Production of hydroxylammonium salt and catalyst thereof | |
| KR102536993B1 (en) | method for tetramine palladium hydrogen carbonate and tetramine palladium hydrogen carbonate manufactured with this | |
| JP3837879B2 (en) | Method for reducing and precipitating metal ions | |
| CN115448352B (en) | Method for preparing cerium dioxide and magnesium fluoride from bastnaesite | |
| CN113321241A (en) | High-valence manganese oxide, preparation method thereof and preparation method of nickel manganese sulfate solution | |
| JP2013067841A (en) | Method for removing copper ion in nickel chloride aqueous solution and method for producing electrolytic nickel | |
| JPH08225862A (en) | Separation and recovery of element of platinum group |
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 |