CN1123843A - Recovery of platinum family elements from waste catalysts - Google Patents
Recovery of platinum family elements from waste catalysts Download PDFInfo
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- CN1123843A CN1123843A CN94118736A CN94118736A CN1123843A CN 1123843 A CN1123843 A CN 1123843A CN 94118736 A CN94118736 A CN 94118736A CN 94118736 A CN94118736 A CN 94118736A CN 1123843 A CN1123843 A CN 1123843A
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Abstract
The process for recovering Pt-family metals from waste catalyst includes such steps as dissolving waste catalyst in solution of sulfuric acid, hydrochloric acid, sodium chlorate and sodium chloride, adsorbing anions of Pt-family metals in solution by using anionic exchange resin, washing the resin with hydrochloric acid or perchloric acid, and reducing the washing liquid with hydrazine hydrate, and features high recovery rate and low cost.
Description
The present invention relates to the solid waste regenerative use technology, particularly a kind of method that from spent catalyst, reclaims the platinum metals.
The platinum group catalyst that is constituted on the carrier of aluminum oxide etc. be will be stated from as the various platinum metals of catalyst component and chemical industry, automobile exhaust gas purifying field etc. will be widely used in.Because the employed platinum metals of this catalyzer costs an arm and a leg, resource shortage, utilize these precious metals imperative again so from used spent catalyst, reclaim also.The recovery technology of developing these noble metals is significant.
The technical study that reclaims platinum metals from be stated from carrier such as aluminum oxide as catalyst component with platinum metals such as platinum, palladiums on the catalyzer that is constituted is more, but applies to industrial few.Existing method can be divided into two kinds of wet method and pyrogenic processes.Also there are some technical problems at present in pyrogenic process, still in the research trial stage; Hydrometallurgic recovery is maximum, the most widely used method of studying both at home and abroad at present.The report of external relevant this respect is many, but has the less of practical value commercial production scale.The domestic method of using in industrial production can reduce two kinds and reclaim technology: a kind of is selective chlorination; Another kind is the carrier dissolution method.
Selective chlorination is to adopt the hydrochloric acid oxidizer that platinum (palladium) is leached, and separates with most of carrier.Still contain a certain amount of platinum metals (being generally 30-50 gram/ton) in the residue of this method after repeatedly chlorination is leached, the rate of recovery is about 95%, and technical process is long, trivial operations, cost height.
The carrier dissolution method adopts sulfuric acid that carrier is dissolved more, and platinum (palladium) is stayed in the slag, reclaims platinum (palladium) then from slag.This method is in the dissolving carrier, and the platinum (palladium) of trace is also along with dissolving, and general platinum content is 3-5mg/l, and the rate of recovery is about 95%, and technical process is long, trivial operations, and precious metal disperses, the cost height.
Also once reported " the complete molten method of catalyzer " abroad, and be about to catalyzer and all dissolve, then platinum metals was separated with carrier.But owing to exist many concrete technical problems, existing processes does not reach due effect.
The method that the purpose of this invention is to provide the recovery platinum metals that a kind of technology is simple, the rate of recovery is high, cost is low, effective.
Method of the present invention is: what will contain the platinum metals is that the catalyzer of carrier is put into the aqueous solution that contains sulfuric acid, hydrochloric acid, sodium chlorate and sodium-chlor with the aluminum oxide, make the dissolving of platinum metals and carrier, pass through anionite-exchange resin then, the platinum metals negatively charged ion is adsorbed onto on the resin, use the hydrochloric acid washing resin, use high chloro acid solution's drip washing resin again, leacheate obtains the platinum metals with hydrazine hydrate reduction.
The preferred weight ratio of the catalyzer of dissolving step described in the inventive method, sulfuric acid, hydrochloric acid, sodium chlorate, sodium-chlor and water is catalyzer: sulfuric acid: hydrogenchloride: sodium chlorate: sodium-chlor: water=1: (2.0-2.8): (0.4-0.8): (0.01-0.03): (0.01-0.03): (2-4).
The hydrochloric acid of described washing usefulness is preferably the hydrochloric acid of 0.05-0.2N; Described washing is preferably the high chloro acid solution of 10-30% (weight) with perchloric acid.
If contain a large amount of carbon in the catalyzer, then after 500-600 ℃ of roasting, dissolve again.
Preferred platiniferous and/or palladium in the described catalyzer.
Described anionite-exchange resin is can the anionic resin in selective adsorption platinum metals.
Method technical process of the present invention is short, and is easy and simple to handle, precious metal rate of recovery height, and production cost is low, is fit to the noble metal catalyst of high low levels.
Solvent for use in the method for the present invention, eluent, reductive agent effect are splendid.
Below can cross embodiment and further specify the present invention and effect thereof.Embodiment:
The spent catalyst that will contain the platinum group metal is removed the charcoal of surface adsorption 500-600 ℃ of roasting.Then by spent catalyst: sulfuric acid: hydrogenchloride: sodium chlorate: sodium-chlor: water is: 1: 2.4: 0.6: 0.016: 0.02: 3 weight ratio mixes, at 4 hours after-filtration of 110 ℃ of reactions, filtrate warp let-off anionite-exchange resin (R410) post, the saturated back of resin 0.1N hydrochloric acid washing resin, use the drip washing of 20% (weight) perchloric acid again, wherein use (Φ 100 * 1000mm) series connection of five posts, four posts exchange, one post drip washing, the about 1.5N of exchange liquid acidity, platinum group metal 150 mg/litre, exchange tail washings platinum group metal＜1 mg/litre, the leacheate after the drip washing gets the platinum metals product with hydrazine hydrate reduction.
Handle typical six batches of spent catalyst with aforesaid method, commercial test results is as follows:
| Lot number | Spent catalyst heavy (kilogram) | Bullion content | Theoretical content (gram) | Product volume | The rate of recovery (%) |
| ?1 | ????75 | Platiniferous 0.35% | 262.5 | ?258.64 | ????98.53 |
| ?2 | ????75 | Platiniferous 0.35% | 262.5 | ?258.20 | ????98.36 |
| ?3 | ????75 | Platiniferous 0.35% | 262.5 | ?258.71 | ????98.56 |
| ?4 | ????75 | Platiniferous 0.35% | 262.5 | ?258.30 | ????98.40 |
| ?5 | ????229 | Platiniferous 0.874 ‰ | 200.23 | ?193.50 | ????96.64 |
| ?6 | ????40 | Contain palladium 0.36 ‰ | 14.4 | ?13.54 | ????94.02 |
Platinum, palladium product purity all reach＞and 99.95%.
Cost recovery: 2.3 yuan/gram platinum; 12.9 unit/gram palladium.
Used anionite-exchange resin is the R410 resin that the Beijing Inst. of Chemical Metallurgy, Ministry of Nuclear Industry produces in this example, this resin is a kind of piperidine derivative, it can be in PPM～a few grams per liter concentration ranges selective adsorption platinum (palladium) etc., platinum complex anion partition ratio on the R410 resin is 600, and the partition ratio of most metal ions such as iron, aluminium, copper, lead, zinc, nickel is 0～3, so be not adsorbed basically concerning these metals.R410 to the adsorptive power of precious metal is: penetrate 90 milligrams of platinum of capacity/gram dried resin: 30 milligrams of palladium/gram dried resins.
Claims (9)
1, a kind of method that from spent catalyst, reclaims the platinum metals, what it is characterized in that containing the platinum metals is that the catalyzer of carrier is put into the aqueous solution that contains sulfuric acid, hydrochloric acid, sodium chlorate and sodium-chlor with the aluminum oxide, make the dissolving of platinum metals and carrier, pass through anionite-exchange resin then, the platinum metals negatively charged ion is adsorbed onto on the resin, use the hydrochloric acid washing resin, use high chloro acid solution's drip washing resin again, leacheate obtains the platinum metals with hydrazine hydrate reduction.
2, the method for claim 1, it is characterized in that the weight proportion catalyzer of described dissolving step: sulfuric acid: hydrogenchloride: sodium chlorate: sodium-chlor: water is 1: (2.0-2.8): (0.4-0.8): (0.01-0.03): (0.01-0.03): (2-4).
3, the method for claim 1, the hydrochloric acid that it is characterized in that described washing usefulness is the hydrochloric acid of 0.05-0.2N.
4, the method for claim 1 is characterized in that described washing perchloric acid is the high chloro acid solution of 10-30% (weight).
5, the method for claim 1 is characterized in that before dissolving step, at the 500-600 ℃ of described catalyzer of roasting.
6, the method for claim 1 is characterized in that containing in the catalyzer platinum.
7, as claim 1 or 6 described methods, it is characterized in that containing in the catalyzer palladium.
8, the method for claim 1 is characterized in that described anionite-exchange resin is the anionic resin in energy selective adsorption platinum metals.
9, method as claimed in claim 8 is characterized in that described resin is a piperidine derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94118736A CN1038199C (en) | 1994-11-30 | 1994-11-30 | Recovery of platinum family elements from waste catalysts |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94118736A CN1038199C (en) | 1994-11-30 | 1994-11-30 | Recovery of platinum family elements from waste catalysts |
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| CN1123843A true CN1123843A (en) | 1996-06-05 |
| CN1038199C CN1038199C (en) | 1998-04-29 |
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| CN94118736A Expired - Fee Related CN1038199C (en) | 1994-11-30 | 1994-11-30 | Recovery of platinum family elements from waste catalysts |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053704C (en) * | 1997-11-03 | 2000-06-21 | 北京有色金属研究总院 | Separation and enrichment process of minute amount of noble metal elements in solution by utilizing carrying fiber column |
| CN1059242C (en) * | 1997-08-28 | 2000-12-06 | 王建国 | Method for recoverying platinum from ammonia oxidation converter waste |
| CN100366770C (en) * | 2003-03-14 | 2008-02-06 | 同和控股（集团）有限公司 | Method for recovering platinum group element |
| CN100447557C (en) * | 2005-03-21 | 2008-12-31 | 吉林大学 | Trace amount gold separated enriching lumination detection device and method |
| CN101509077B (en) * | 2009-02-19 | 2010-08-25 | 昆明贵金属研究所 | Method for extracting platinum, palladium, rhodium from automotive catalyst of ore phase reconstruction |
| CN102766767A (en) * | 2012-07-20 | 2012-11-07 | 佛山市邦普循环科技有限公司 | Ion exchange recovery method for precious metal platinum in spent automobile exhaust catalyst |
| CN103276215A (en) * | 2013-06-03 | 2013-09-04 | 贵研资源（易门）有限公司 | Method for recovering noble metal from waste catalyst |
| CN103502484A (en) * | 2011-03-09 | 2014-01-08 | Rti化学工程有限公司 | Method for recovering platinum group metals from industrial waste containing platinum group metals |
| CN105256136A (en) * | 2015-11-18 | 2016-01-20 | 金川集团股份有限公司 | Method of separating platinum group metals from platinum group metal feed liquid |
| CN106086452A (en) * | 2016-08-09 | 2016-11-09 | 成都虹华环保科技股份有限公司 | A kind of Palladium recovery device |
| CN106086454A (en) * | 2016-08-12 | 2016-11-09 | 陈永福 | A kind of technique being enriched with platinum group metal and gold |
| CN107190147A (en) * | 2017-05-26 | 2017-09-22 | 核工业北京化工冶金研究院 | A kind of method that selective dissolution from platinum-containing waste catalyst reclaims platinum |
| CN107267772A (en) * | 2017-05-26 | 2017-10-20 | 核工业北京化工冶金研究院 | A kind of method that platinum and rhenium are reclaimed in the platinum-rhenium reforming catalyst from aluminium base |
| CN108265180A (en) * | 2017-12-28 | 2018-07-10 | 核工业北京化工冶金研究院 | The leaching method of platinum, palladium, rhodium in useless three-way catalyst |
| CN110499421A (en) * | 2019-08-22 | 2019-11-26 | 西安凯立新材料股份有限公司 | A kind of platinum group metal circular regeneration technique |
| CN112029998A (en) * | 2020-08-27 | 2020-12-04 | 郴州高鑫材料有限公司 | Method for recovering platinum group metal from granular waste catalyst by combination of dissolution, absorption and desorption |
| CN112442600A (en) * | 2020-12-02 | 2021-03-05 | 中南大学 | Method for recovering platinum group metal from waste three-way catalyst |
| CN114058849A (en) * | 2021-11-03 | 2022-02-18 | 核工业北京化工冶金研究院 | Method for recovering platinum and aluminum from aluminum-based platinum catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400684C (en) * | 2006-05-19 | 2008-07-09 | 中国石油化工股份有限公司 | Method for recovering noble-metal from waste catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307123A (en) * | 1987-06-08 | 1988-12-14 | Tanaka Kikinzoku Kogyo Kk | Method for recovering pt group metal from nitric acid solution |
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1994
- 1994-11-30 CN CN94118736A patent/CN1038199C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059242C (en) * | 1997-08-28 | 2000-12-06 | 王建国 | Method for recoverying platinum from ammonia oxidation converter waste |
| CN1053704C (en) * | 1997-11-03 | 2000-06-21 | 北京有色金属研究总院 | Separation and enrichment process of minute amount of noble metal elements in solution by utilizing carrying fiber column |
| CN100366770C (en) * | 2003-03-14 | 2008-02-06 | 同和控股（集团）有限公司 | Method for recovering platinum group element |
| CN100447557C (en) * | 2005-03-21 | 2008-12-31 | 吉林大学 | Trace amount gold separated enriching lumination detection device and method |
| CN101509077B (en) * | 2009-02-19 | 2010-08-25 | 昆明贵金属研究所 | Method for extracting platinum, palladium, rhodium from automotive catalyst of ore phase reconstruction |
| CN103502484A (en) * | 2011-03-09 | 2014-01-08 | Rti化学工程有限公司 | Method for recovering platinum group metals from industrial waste containing platinum group metals |
| CN102766767A (en) * | 2012-07-20 | 2012-11-07 | 佛山市邦普循环科技有限公司 | Ion exchange recovery method for precious metal platinum in spent automobile exhaust catalyst |
| CN103276215A (en) * | 2013-06-03 | 2013-09-04 | 贵研资源（易门）有限公司 | Method for recovering noble metal from waste catalyst |
| CN103276215B (en) * | 2013-06-03 | 2014-08-20 | 贵研资源（易门）有限公司 | Method for recovering noble metal from waste catalyst |
| CN105256136A (en) * | 2015-11-18 | 2016-01-20 | 金川集团股份有限公司 | Method of separating platinum group metals from platinum group metal feed liquid |
| CN106086452A (en) * | 2016-08-09 | 2016-11-09 | 成都虹华环保科技股份有限公司 | A kind of Palladium recovery device |
| CN106086452B (en) * | 2016-08-09 | 2017-11-07 | 成都虹华环保科技股份有限公司 | A kind of Palladium recovery device |
| CN106086454A (en) * | 2016-08-12 | 2016-11-09 | 陈永福 | A kind of technique being enriched with platinum group metal and gold |
| CN107190147A (en) * | 2017-05-26 | 2017-09-22 | 核工业北京化工冶金研究院 | A kind of method that selective dissolution from platinum-containing waste catalyst reclaims platinum |
| CN107267772A (en) * | 2017-05-26 | 2017-10-20 | 核工业北京化工冶金研究院 | A kind of method that platinum and rhenium are reclaimed in the platinum-rhenium reforming catalyst from aluminium base |
| CN107190147B (en) * | 2017-05-26 | 2019-05-17 | 核工业北京化工冶金研究院 | A method of selective dissolution recycles platinum from platinum-containing waste catalyst |
| CN108265180A (en) * | 2017-12-28 | 2018-07-10 | 核工业北京化工冶金研究院 | The leaching method of platinum, palladium, rhodium in useless three-way catalyst |
| CN110499421A (en) * | 2019-08-22 | 2019-11-26 | 西安凯立新材料股份有限公司 | A kind of platinum group metal circular regeneration technique |
| CN112029998A (en) * | 2020-08-27 | 2020-12-04 | 郴州高鑫材料有限公司 | Method for recovering platinum group metal from granular waste catalyst by combination of dissolution, absorption and desorption |
| CN112442600A (en) * | 2020-12-02 | 2021-03-05 | 中南大学 | Method for recovering platinum group metal from waste three-way catalyst |
| CN114058849A (en) * | 2021-11-03 | 2022-02-18 | 核工业北京化工冶金研究院 | Method for recovering platinum and aluminum from aluminum-based platinum catalyst |
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| Publication number | Publication date |
|---|---|
| CN1038199C (en) | 1998-04-29 |
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