CN104178641A - Method for recovering rhodium from waste rhodium plating solution - Google Patents
Method for recovering rhodium from waste rhodium plating solution Download PDFInfo
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- CN104178641A CN104178641A CN201410425297.6A CN201410425297A CN104178641A CN 104178641 A CN104178641 A CN 104178641A CN 201410425297 A CN201410425297 A CN 201410425297A CN 104178641 A CN104178641 A CN 104178641A
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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
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Abstract
The invention discloses a method for recovering rhodium from a waste rhodium plating solution. The method is characterized by comprising the following steps: adding solid alkali to the waste rhodium plating solution until the pH of the solution is 8-10 so that rhodium is participated in a form of rhodium hydroxide; dissolving sediments by hydrochloric acid after solid-liquid separation, thereby obtaining a rhodium solution; removing cation impurities by ion exchange, resolving to obtain a pure rhodium chloride acid solution; adjusting the pH of the pure rhodium chloride acid solution to be 6-7, slowly adding hydrazine hydrate, boiling and restoring to obtain rhodium black; and restoring the rhodium black in a hydrogen reduction furnace, wherein the reduction temperature is 700-800 DEG C, and the time is 2-3 hours, thereby obtaining pure rhodium powder, wherein the recovery rate of rhodium is greater than 94%, and the purity is 99.95%. The method has the advantages of simple technological process, high rhodium recovery rate and low cost.
Description
Technical field
The present invention relates to a kind of method that reclaims precious metal from precious metal waste liquid, be specifically related to reclaim in a kind of useless rhodium electroplating solution producing the method for rhodium from rhodium electroplating process.
Background technology
Rhodium has unique physical and chemical performance, matter is hard and crisp, chemical stability is very high, under moderate temperature, it is not dissolved by chloroazotic acid and most of acid, 200～600 ℃ can with hot concentrated sulfuric acid, hot Hydrogen bromide, clorox and free halogen react with, with many molten metals, as the alkali Fails To Respond of gold and silver, sodium and potassium and melting.Rhodium plating is silvery white in color, have that reflectivity is high, wear resistance good, contact resistance is little, good conductivity, feature that chemical stability is high, in fields such as opticinstrument (as chemical apparatus, reflective mirror, microscopical reflecting coating), electrical equipment industry (on as the Surface Contact layer on wireless or audio frequency, printed circuit board the wearing layer of connector assembly and as ornament layer, anti-silver-colored photochromic layer etc.), processing of ornaments, be widely used.The main salt of rhodium electroplating solution has the ammino compound of rhodium sulfate, phosphoric acid rhodium, phosphoric acid, rhodium sulfate, perchloric acid rhodium, thionamic acid rhodium, fluoroboric acid rhodium, rhodium chloride etc.Reaching its maturity, applying of water-soluble rhodium plating technology is increasingly extensive, and the consequent is a large amount of useless rhodium electroplating solution.From rhodium plating waste liquid, reclaim rhodium and there is significant economic benefit.From rhodium plating liquid, reclaim at present the multiplex metal replacement method of rhodium, substitution product obtains pure rhodium product with carrying out refining after dissolving with hydrochloric acid displacement metal again, is again prepared as corresponding compound multiplexing.Its shortcoming is, metal consumption is difficult to accurately grasp, and it is many that substitution product is carried metal secretly, during separated displacement metal, may cause the twice dispersing loss of rhodium, substitution product is easily fine suspended state, and more difficult rapid subsidence is assembled, and may affect the rate of recovery of rhodium during solid-liquid separation.
Summary of the invention
The object of the invention is the recovery problem for the useless rhodium electroplating solution producing in rhodium electroplating process, proposed a kind of method that reclaims rhodium from useless rhodium electroplating solution, technical process of the present invention is simple, and the rhodium rate of recovery is high, and cost is low.
In the present invention includes, close precipitation, separated and dissolved, hydrazine hydrate reduction, 4 steps of hydrogen reduction:
1. neutralization precipitation: solid alkali (any one in sodium hydroxide, potassium hydroxide) is joined in useless rhodium electroplating solution, and regulator solution pH=8～10, make in electroplate liquid rhodium with rhodium hydroxide form precipitation completely;
2. separated and dissolved: by rhodium hydroxide precipitation dissolving with hydrochloric acid, rhodium is existed with chlorine rhodium complex anion form, then by ion exchange resin, the positively charged ion in solution is removed, obtain pure rhodium chloride acid solution after resolving.
3. hydrazine hydrate reduction: adjust pH=6～7 of the pure rhodium chloride acid solution of gained, control at 90～100 ℃ of temperature and slowly add hydrazine hydrate to boil reduction, obtain rhodium black;
4. hydrogen reduction: rhodium black is reduced in hydrogen reduction furnace, and reduction temperature is 700～800 ℃, and the recovery time is 2～3h, obtains High Purity Rhodium powder;
The present invention realizes the high efficiente callback of the metal rhodium in electroplate liquid, makes High Purity Rhodium powder, and technical process is simple, and the rhodium rate of recovery is high, and cost is low.The rhodium powder purity that adopts the inventive method to prepare gained is 99.95%, and the rate of recovery of rhodium is greater than 94%.
Accompanying drawing explanation
Accompanying drawing Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1, referring to accompanying drawing 1, by the useless rhodium electroplating solution neutralization precipitation of 1L: solid sodium hydroxide is joined in useless rhodium electroplating solution, and regulator solution pH=9, obtains rhodium hydroxide precipitation; After solid-liquid separation, by the rhodium hydroxide precipitation dissolving with hydrochloric acid of gained, through ion-exchange, remove cation impurity, after resolving, obtain pure rhodium chloride acid solution; Then adjust pH value of solution=7, add after hydrazine hydrate boils reduction and obtain rhodium black; Rhodium black reduces in hydrogen reduction furnace, and reduction temperature is 700 ℃, and the recovery time is 3h, obtains pure rhodium powder.The rate of recovery of rhodium is greater than 94%, rhodium powder purity 99.95%.
Embodiment 2, referring to accompanying drawing 1, by the useless rhodium electroplating solution neutralization precipitation of 1L: solid potassium hydroxide is joined in useless rhodium electroplating solution, and regulator solution pH=9, obtains rhodium hydroxide precipitation; After solid-liquid separation, by the rhodium hydroxide precipitation dissolving with hydrochloric acid of gained, through ion-exchange, remove cation impurity, after resolving, obtain pure rhodium chloride acid solution; Then adjust pH value of solution=7, add after hydrazine hydrate boils reduction and obtain rhodium black; Rhodium black reduces in hydrogen reduction furnace, and reduction temperature is 700 ℃, and the recovery time is 3h, obtains pure rhodium powder.The rate of recovery of rhodium is greater than 94%, rhodium powder purity 99.95%.
Embodiment 3, referring to accompanying drawing 1, by the useless rhodium electroplating solution neutralization precipitation of 1L: solid sodium hydroxide is joined in useless rhodium electroplating solution, and regulator solution pH=10, obtains rhodium hydroxide precipitation; After solid-liquid separation, by the rhodium hydroxide precipitation dissolving with hydrochloric acid of gained, through ion-exchange, remove cation impurity, after resolving, obtain pure rhodium chloride acid solution; Then adjust pH value of solution=6, add after hydrazine hydrate boils reduction and obtain rhodium black; Rhodium black reduces in hydrogen reduction furnace, and reduction temperature is 800 ℃, and the recovery time is 2h, obtains pure rhodium powder.The rate of recovery of rhodium is greater than 94%, rhodium powder purity 99.95%.
Claims (4)
1. from useless rhodium electroplating solution, reclaim the method for rhodium, it is characterized in that comprising following processing step:
1. neutralization precipitation: solid alkali is joined in useless rhodium electroplating solution, and regulator solution pH value, makes rhodium in electroplate liquid precipitate with rhodium hydroxide form;
2. separated and dissolved: by step 1. the rhodium hydroxide precipitation of gained with acid, dissolve, then go out foreign ion by ion-exchange, after resolving, obtain pure rhodium chloride acid solution;
3. hydrazine hydrate reduction: set-up procedure is the pH value of the pure rhodium chloride acid solution of gained 2., adds hydrazine hydrate to boil reduction and obtains rhodium black;
4. hydrogen reduction: by step 3. the rhodium black of gained in hydrogen reduction furnace, reduce, obtain pure rhodium powder.
2. the method that reclaims rhodium from useless rhodium electroplating solution according to claim 1, it is characterized in that step 1. described solid alkali be any one in sodium hydroxide, potassium hydroxide.
3. the method that reclaims rhodium from useless rhodium electroplating solution according to claim 1, is characterized in that 1. described adjustment pH value of solution=8～10 of step.
4. the method that reclaims rhodium from useless rhodium electroplating solution according to claim 1, is characterized in that the acid described in step is 2. hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410425297.6A CN104178641A (en) | 2014-08-27 | 2014-08-27 | Method for recovering rhodium from waste rhodium plating solution |
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| CN201410425297.6A CN104178641A (en) | 2014-08-27 | 2014-08-27 | Method for recovering rhodium from waste rhodium plating solution |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105177306A (en) * | 2015-09-14 | 2015-12-23 | 昆明贵金属研究所 | Method for recycling rhodium from sulfuric acid type rhodanized waste liquid |
| CN107406908A (en) * | 2015-03-05 | 2017-11-28 | 贺利氏德国有限责任两合公司 | The method for producing elemental rhodium |
| CN107641720A (en) * | 2017-08-25 | 2018-01-30 | 金川集团股份有限公司 | A kind of method of the segmentation recovery noble metal from waste liquid containing noble metal |
| CN111057862A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Preparation method of high-purity rhodium wire for self-powered neutron detector |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
| 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 |
| CN113020615A (en) * | 2021-03-03 | 2021-06-25 | 中海油(山西)贵金属有限公司 | Method for preparing high-purity rhodium powder by using rhodium trichloride |
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| CN1031567A (en) * | 1987-08-13 | 1989-03-08 | 中国有色金属工业总公司昆明贵金属研究所 | The dissolving and the purification of thick rhodium and high rhodium-containing alloyed scrap |
| CN101260469A (en) * | 2008-04-21 | 2008-09-10 | 上海大学 | Method for reclaiming and purifying platinum and rhodium from waste material containing platinum and rhodium |
| CN101941739A (en) * | 2010-09-20 | 2011-01-12 | 中国海洋石油总公司 | Method for preparing high-purity hydrated rhodium trichloride |
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2014
- 2014-08-27 CN CN201410425297.6A patent/CN104178641A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1031567A (en) * | 1987-08-13 | 1989-03-08 | 中国有色金属工业总公司昆明贵金属研究所 | The dissolving and the purification of thick rhodium and high rhodium-containing alloyed scrap |
| CN101260469A (en) * | 2008-04-21 | 2008-09-10 | 上海大学 | Method for reclaiming and purifying platinum and rhodium from waste material containing platinum and rhodium |
| CN101941739A (en) * | 2010-09-20 | 2011-01-12 | 中国海洋石油总公司 | Method for preparing high-purity hydrated rhodium trichloride |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107406908A (en) * | 2015-03-05 | 2017-11-28 | 贺利氏德国有限责任两合公司 | The method for producing elemental rhodium |
| CN107406908B (en) * | 2015-03-05 | 2019-12-10 | 贺利氏德国有限责任两合公司 | Method for producing elemental rhodium |
| CN105177306A (en) * | 2015-09-14 | 2015-12-23 | 昆明贵金属研究所 | Method for recycling rhodium from sulfuric acid type rhodanized waste liquid |
| CN107641720A (en) * | 2017-08-25 | 2018-01-30 | 金川集团股份有限公司 | A kind of method of the segmentation recovery noble metal from waste liquid containing noble metal |
| CN107641720B (en) * | 2017-08-25 | 2019-12-31 | 金川集团股份有限公司 | Method for sectionally recovering precious metals from precious metal-containing waste liquid |
| CN111057862A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Preparation method of high-purity rhodium wire for self-powered neutron detector |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
| CN111057862B (en) * | 2019-12-09 | 2022-04-12 | 重庆材料研究院有限公司 | Preparation method of high-purity rhodium wire for self-powered neutron detector |
| CN111054933B (en) * | 2019-12-09 | 2022-08-02 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
| 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 |
| CN111996386B (en) * | 2020-08-28 | 2021-06-29 | 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 |
| CN113020615A (en) * | 2021-03-03 | 2021-06-25 | 中海油(山西)贵金属有限公司 | Method for preparing high-purity rhodium powder by using rhodium trichloride |
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Application publication date: 20141203 |