CN104831073A - Technology for recovering platinum, palladium and rhodium from spent auto-catalyst - Google Patents
Technology for recovering platinum, palladium and rhodium from spent auto-catalyst Download PDFInfo
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Abstract
A technology for recovering platinum, palladium and rhodium from a spent auto-catalyst comprises the following steps: pre-processing, enriching, removing impurities, separating, and purifying to obtain relevant platinum, palladium and rhodium products. The technology has the following advantages: environment protection in the whole flow from preprocessing to enriched platinum, palladium and rhodium separation and purification and product discharge is good; the technology has good process continuity, simple flow, and high platinum, palladium and rhodium separation and purification efficiency; and in the recovery process, the direct recovery rate of platinum is not lower than 91%, and the direct recovery rate of palladium is not lower than 95%.
Description
Technical field
The invention belongs to metallic substance extractive technique field, particularly relate to the technique reclaiming platinum, palladium, rhodium from spent auto-catalysts.
Background technology
Platinum, palladium, rhodium 3 elements (hereinafter referred to as platinum metals) have unique physics-chem characteristic because of it, have a wide range of applications in Aeronautics and Astronautics, navigation, guided missile, rocket, nuclear power, microelectronics, chemical, petrochemical complex, glass fibre, waste-gas cleaning and metallurgical industry every field, become modern industry, military project and new high-tech industry important materials, have the title of " modern industry vitamin b6 usp ".
In recent years, China's platinum metals consumption maintains sustained and rapid growth, and is increased to current tens tons by former several tons.But China's platinum metals mineral products resource is seriously deficient, be in the state that need satisfy the demands by import for a long time.Along with the development of China's economy science and technology, China will continue to rise to the demand of platinum metals and import volume.The platinum metals product of substantial amounts, after using and losing efficacy, by producing a large amount of platinum metals secondary resources, reclaiming platinum metals, having very important strategic importance to the wretched insufficiency making up China's platinum metals mineral products resource from these secondary resources.
Automobile spent catalyst is important platinum metals secondary resource, and according to reports, 2014 or produced spent auto-catalysts 5000 tons, platinum, palladium, rhodium content was more than 6 tons, and how efficient recovery platinum metals wherein obtains the extensive concern of insider.
Traditional technology main method is to raw material process potassium cloride, and the content obtaining leached mud platinum, palladium, rhodium is about 100-300g/t, and leached mud, again by wet method or thermal process, extracts platinum metals wherein further.The platinum, palladium, rhodium mixed solution obtained, thioether 30%S201+20% diethylbenzene+50% n-dodecane oil extraction agent extraction Pd can be adopted, finally palladium sponge is reduced into after strip liquor refining, TBP extracts Pt, obtain spongy platinum after strip liquor refining, the rhodium solution removal of impurities purification post-treatment of the not platiniferous palladium finally obtained becomes related products.This operational path is comparatively ripe, effectively can extract platinum, palladium, rhodium and realize platinum, palladium, rhodium and be separated from spent auto-catalysts, direct yield, the rate of recovery and product purity can reach good result, but also exist that platinum metals primary recovery is low, leaching process operation is many, the deficiency such as extraction and refining process complicated and time consumption, cause that longer, reagent consumption whole return period is large and cost of labor cost is high, production line investment is high.
Increasingly competitive along with spent auto-catalysts market, raw materials cost is also more and more higher, adopt traditional technology to reclaim platinum, palladium, rhodium and can not obtain desirable economic benefit, many domestic enterprises are often inferior to other developed country in raw material competition, cause important national strategy resource-platinum metals to be run off external.Scientific and technical competition has been transferred in the competition of raw material, and the platinum metals new recovering technology that research environment protects, the rate of recovery is high, return period is short, cost is low becomes one of the most popular research topic.
Beneficiation technologies comparatively advanced in the world is at present plasma heating furnace pyrometallurgical smelting beneficiation technologies, and isolation technique is molecular recognition technology.The advantage of plasma heating furnace is that the rate of recovery is high, and processing speed is fast, but has high input, high material consumption; Molecular recognition technology is applied in platinum, palladium, rhodium and is separated, and can replace traditional abstraction technique, make platinum, palladium, rhodium realize high efficiency separation.
For this reason, above-mentioned deficiency be overcome, need to invent a kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts, determine concrete technology parameter.
Summary of the invention
For overcoming above defect, a kind of beneficial effect reclaiming the technique of platinum, palladium, rhodium from spent auto-catalysts of the present invention is: effectively solve spent auto-catalysts wet processing leaching yield low, leached mud content is high, needs the problem extracted further, significantly reduces production cost and improves organic efficiency; Traditional Sodium Nitrite complexometry is avoided to produce the problem of a large amount of serious environment pollution oxynitride; The platinum palladium solution obtained after heavy rhodium adopts the acting in conjunction of ammoniacal liquor ammonium chloride, and make platinum palladium realize good separation, production efficiency is high, and direct yield is high; Platinum, palladium, rhodium is separated the technique of separating platinum palladium while of employing after first separate rhodium, platinum, palladium, rhodium purification process almost can carry out simultaneously, avoid the loaded down with trivial details tediously long operation of first extraction of palladium Extraction of Platinum again, improve production efficiency largely and reduce the productive manpower and reagent cost.
From spent auto-catalysts, reclaim a technique for platinum, palladium, rhodium, it is characterized in that: the described technique reclaiming platinum, palladium, rhodium from spent auto-catalysts is as follows:
Main process route divides four steps, and spent auto-catalysts first carries out pre-treatment, after carry out enrichment, carry out removal of impurities afterwards, after removal of impurities, be separated refining, obtain the product of relevant platinum, palladium, rhodium.
(1) pre-treatment
Spent auto-catalysts is through pulverizing and sieving, and crossing grit number is more than 200 orders, and screen overflow returns continuation grinding and sieving, screen underflow carries out sulfuric acid acid etching, sulfuric acid acid etching temperature is 200-300 DEG C, and sulfuric acid concentration is the acid etching material that 50-98% obtains, for enrichment operation;
The process that pulverizes and sieves is by blower fan exhausting and bag collection, and in acid corrosion process, equipment is airtight, and the gas of generation enters 3 grades of absorptions by exhausting, and first 2 grades is water absorption liquid, and the third stage is 20% sodium hydroxide absorption liquid, and the sour water absorption liquid of generation returns acid etching and uses;
(2) enrichment
Acid etching material carries out secondary potassium cloride, and leach liquor displacement obtains platinum, palladium, rhodium replacement slag, and leached mud is stacked and stored:
Secondary potassium cloride: salt acidacidity 8mol/L, liquid-solid ratio 5-8:1ml/g, extraction temperature 75-90 DEG C, time 2-4 hour,
Iron replacement: temperature 40-70 DEG C, acidity 2-6mol/L, displacement terminal is as the criterion to detect Pt, Pd, Rh content Jun≤below 0.0005g/L;
Aluminium powder is replaced: temperature 20-50 DEG C, acidity 2-6mol/L, and displacement terminal is as the criterion to detect Pt, Pd, Rh content Jun≤below 0.0005g/L;
(3) removal of impurities
Replacement slag is after dissolving liquid making, and through resin cation (R.C.) removal of impurity metallic cation, the removal of impurities liquid of acquisition is used for next step separating-purifying, and insoluble slag returns liquid making and dissolves:
Dissolving liquid making adopts hydrochloric acid+oxygenant to dissolve: salt acidacidity 8-10mol/L, temperature 70-90 DEG C, redox potential 700-900mv, dissolution time 2-4 hour;
Zeo-karb regenerated liquid adopts hydrochloric acid soln, acidity 6-10mol/L, and after regeneration, Zeo-karb is reusable, and regenerated liquid is replaced, the unified process of replacement slag;
(4) separating-purifying
Removal of impurities liquid is heavy rhodium after concentrated, and heavy rhodium adopts organic sulfide to carry out selectivity to sink rhodium, and namely concentrated solution controls conditions suitable and directly carries out heavy rhodium, and first realize the separation of rhodium, rhodium precipitation can obtain relevant rhodium product after simple refining;
After heavy rhodium, liquid is by adding ammonium chloride and ammoniacal liquor complexing, and ammonium chloride add-on is 0.1-1 times of platinum, and ammoniacal liquor add-on is as the criterion to control solution PH 6-8, and palladium generates the sub-palladium of solubility dichloro four ammonium network, and platinum generates ammonium chloroplatinate precipitate, realizes the separation of platinum palladium; Palladium, by traditional ammoniacal liquor complexing---hcl acidifying method carries out refining, three times repeatedly, is finally reduced into palladium sponge; Platinum carries out refining by traditional ammonium chloroplatinate repeated precipitation process, three times repeatedly, is finally reduced into spongy platinum; Platinum palladium refining slag returns liquid making system.
A kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts of the present invention; its positively effect is: from pre-treatment to the separation refining and the product output that are enriched to platinum, palladium, rhodium; whole workflow environment protects; technique connecting is good; flow process is simple; platinum, palladium, rhodium separating-purifying efficiency is high, in process the straight Shou of platinum Shuai≤91%, the straight Shou of palladium to Shuai≤95%.
Accompanying drawing explanation
A kind of process flow sheet reclaiming platinum, palladium, rhodium from spent auto-catalysts of Fig. 1.
Fig. 2 pretreatment technology schema.
Fig. 3 process of enriching schema.
Fig. 4 impurity removing process figure.
Fig. 5 platinum, palladium, rhodium process for separating and purifying schema.
Embodiment
Embodiment one:
(1) pre-treatment
Spent auto-catalysts is through pulverizing and sieving, and crossing grit number is 205 orders, and screen overflow returns continuation grinding and sieving, and screen underflow carries out sulfuric acid acid etching, and sulfuric acid acid etching temperature is 250 DEG C, and sulfuric acid concentration is the 65% acid etching material obtained, for enrichment operation;
The process that pulverizes and sieves is by blower fan exhausting and bag collection, and in acid corrosion process, equipment is airtight, and the gas of generation enters 3 grades of absorptions by exhausting, and first 2 grades is water absorption liquid, and the third stage is 20% sodium hydroxide absorption liquid, and the sour water absorption liquid of generation returns acid etching and uses;
(2) enrichment
Acid etching material carries out secondary potassium cloride, and leach liquor displacement obtains platinum, palladium, rhodium replacement slag, and leached mud is stacked and stored;
Secondary potassium cloride: salt acidacidity 8mol/L, liquid-solid ratio 6:1ml/g, extraction temperature 80 DEG C, 3 hours time;
Iron replacement: temperature 50 C, acidity 4mol/L, displacement terminal is as the criterion to detect Pt, Pd, Rh content for 0.0003g/L;
Aluminium powder is replaced: temperature 40 DEG C, acidity 4mol/L, and displacement terminal is as the criterion to detect Pt, Pd, Rh content for 0.0004g/L;
(3) removal of impurities
Replacement slag is after dissolving liquid making, and through resin cation (R.C.) removal of impurity metallic cation, the removal of impurities liquid of acquisition is used for next step separating-purifying, and insoluble slag returns liquid making and dissolves:
Dissolving liquid making adopts hydrochloric acid+oxygenant to dissolve; Salt acidacidity 9mol/L, temperature 80 DEG C, redox potential 750mv, dissolution time 3 hours;
Zeo-karb regenerated liquid adopts hydrochloric acid soln, acidity 8mol/L, and after regeneration, Zeo-karb is reusable, and regenerated liquid is replaced, the unified process of replacement slag;
(4) separating-purifying
Removal of impurities liquid is heavy rhodium after concentrated, and heavy rhodium adopts many sulfur organics to carry out selectivity to sink rhodium, rhodium content 3g/L, acidity 6mol/L in solution, and temperature 60 C carries out heavy rhodium, first realizes the separation of rhodium, and rhodium precipitation obtains rhodium product after simple refining;
After heavy rhodium, liquid is by adding ammonium chloride and ammoniacal liquor complexing, and ammonium chloride add-on is 0.5 times of platinum, and ammoniacal liquor add-on is as the criterion to control solution PH 7, and palladium generates the sub-palladium of solubility dichloro four ammonium network, and platinum generates ammonium chloroplatinate precipitate, realizes the separation of platinum palladium; Palladium, by traditional ammoniacal liquor complexing---hcl acidifying method carries out refining, three times repeatedly, is finally reduced into palladium sponge; Platinum carries out refining by traditional ammonium chloroplatinate repeated precipitation process, three times repeatedly, is finally reduced into spongy platinum; Platinum palladium refining slag returns liquid making system.
Claims (1)
1. from spent auto-catalysts, reclaim a technique for platinum, palladium, rhodium, it is characterized in that: the described technique reclaiming platinum, palladium, rhodium from spent auto-catalysts is as follows:
(1) pre-treatment
Spent auto-catalysts adopts and pulverizes and sieves, and crossing grit number is more than 200 orders, for the first time after pulverization process, screen overflow returns, and continue grinding and sieving, screen underflow carries out sulfuric acid acid etching, sulfuric acid acid etching temperature is 200-300 DEG C, and sulfuric acid concentration is 50-98%, obtains acid etching material;
The process that pulverizes and sieves uses blower fan exhausting and bag collection, in acid corrosion process, equipment is airtight, and the gas of generation enters 3 grades of tail gas absorbing systems by exhausting, and first 2 grades is water absorption liquid, the third stage is 20% sodium hydroxide absorption liquid, and the sour water absorption liquid of generation returns acid etching and uses;
(2) enrichment
Acid etching material carries out secondary potassium cloride, and leach liquor displacement adopts iron replacement or the displacement of aluminium slag, obtains platinum, palladium, rhodium replacement slag after displacement, and replacement slag is stacked and stored;
Secondary potassium cloride: salt acidacidity 8mol/L, liquid-solid ratio 5-8:1ml/g, extraction temperature 75-90 DEG C, time 2-4 hour;
Iron replacement: temperature 40-70 DEG C, acidity 2-6mol/L, displacement terminal is as the criterion to detect Pt, Pd, Rh content Jun≤below 0.0005g/L;
Aluminium powder is replaced: temperature 20-50 DEG C, acidity 2-6mol/L, and displacement terminal is as the criterion to detect Pt, Pd, Rh content Jun≤below 0.0005g/L;
(3) removal of impurities
Replacement slag is after dissolving liquid making, and the impurity cationic in Zeo-karb removing solution, obtains comparatively pure precious metal removal of impurities liquid, and for next step separating-purifying, insoluble slag returns liquid making and dissolves;
Dissolving liquid making adopts hydrochloric acid+oxygenant to dissolve; Salt acidacidity 8-10mol/L, temperature 70-90 DEG C, redox potential 700-900mv, dissolution time 2-4 hour;
Zeo-karb regenerated liquid adopts hydrochloric acid soln, acidity 6-10mol/L, and after regeneration, Zeo-karb is recycling, and regenerated liquid is replaced, the unified process of replacement slag;
(4) separating-purifying
Heavy rhodium after removal of impurities liquid is concentrated, heavy rhodium adopts many sulfur organics to carry out selectivity to sink rhodium, and in solution, rhodium content is not less than 2g/L, acidity 0.5-8mol/L, temperature 40-90 DEG C is carried out heavy rhodium, first realizes the separation of rhodium, and rhodium precipitation can obtain rhodium product after simple refining;
After heavy rhodium, liquid is by adding ammonium chloride and ammoniacal liquor complexing, and ammonium chloride add-on is 0.1-1 times of platinum, and ammoniacal liquor add-on is as the criterion to control solution PH 6-8, and palladium generates the sub-palladium of solubility dichloro four ammonium network, and platinum generates ammonium chloroplatinate precipitate, realizes the separation of platinum palladium; Palladium, by traditional ammoniacal liquor complexing---hcl acidifying method carries out refining, three times repeatedly, is finally reduced into palladium sponge; Platinum carries out refining by traditional ammonium chloroplatinate repeated precipitation process, three times repeatedly, is finally reduced into spongy platinum; Platinum palladium refining slag returns liquid making system.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105256145A (en) * | 2015-11-18 | 2016-01-20 | 金川集团股份有限公司 | Method for extracting noble metal from waste vehicle exhaust catalyst |
| CN106222437A (en) * | 2016-08-29 | 2016-12-14 | 金川集团股份有限公司 | A kind of method of refine palladium from alkalescence strip liquor |
| CN106367611A (en) * | 2016-09-13 | 2017-02-01 | 中南大学 | Method for separating enriched palladium from waste Pd/Al2O3 catalyst chloride leaching solution |
| 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 |
| CN107326183A (en) * | 2017-06-19 | 2017-11-07 | 荆门市格林美新材料有限公司 | The method that the efficient impurity elimination of abandoned car tai-gas clean-up catalyst carries palladium |
| CN107574303A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of hydrazine hydrate reduction automobile spent catalyst |
| CN110016555A (en) * | 2019-05-14 | 2019-07-16 | 贵研资源（易门）有限公司 | Precious metal separation method of purification in solution |
| 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 |
| CN112831670A (en) * | 2019-11-25 | 2021-05-25 | 荆门市格林美新材料有限公司 | Method for recovering platinum, palladium and rhodium from automobile exhaust waste catalyst |
| CN113564379A (en) * | 2021-07-26 | 2021-10-29 | 福建有道贵金属材料科技有限公司 | Method for recovering precious metal from spent automobile catalyst |
| CN114231749A (en) * | 2021-12-28 | 2022-03-25 | 金川集团股份有限公司 | Method for recovering platinum and rhodium from platinum and rhodium-containing waste liquid |
| CN115612855A (en) * | 2021-07-14 | 2023-01-17 | 谷育英 | Method for recovering metal platinum from platinum-containing waste catalyst |
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2015
- 2015-05-04 CN CN201510220184.7A patent/CN104831073B/en not_active Expired - Fee Related
Non-Patent Citations (1)
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| 王金利等: "国内废催化剂中铂的回收及提纯技术", 《化学工业与工程技术》 * |
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| CN105256145A (en) * | 2015-11-18 | 2016-01-20 | 金川集团股份有限公司 | Method for extracting noble metal from waste vehicle exhaust catalyst |
| CN106222437A (en) * | 2016-08-29 | 2016-12-14 | 金川集团股份有限公司 | A kind of method of refine palladium from alkalescence strip liquor |
| CN106222437B (en) * | 2016-08-29 | 2018-04-10 | 金川集团股份有限公司 | A kind of method that palladium is refined from alkaline strip liquor |
| CN106367611A (en) * | 2016-09-13 | 2017-02-01 | 中南大学 | Method for separating enriched palladium from waste Pd/Al2O3 catalyst chloride leaching solution |
| CN107574303A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of hydrazine hydrate reduction automobile spent catalyst |
| 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 |
| 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 |
| CN107326183A (en) * | 2017-06-19 | 2017-11-07 | 荆门市格林美新材料有限公司 | The method that the efficient impurity elimination of abandoned car tai-gas clean-up catalyst carries palladium |
| CN110016555A (en) * | 2019-05-14 | 2019-07-16 | 贵研资源（易门）有限公司 | Precious metal separation method of purification in solution |
| CN112831670A (en) * | 2019-11-25 | 2021-05-25 | 荆门市格林美新材料有限公司 | Method for recovering platinum, palladium and rhodium from automobile exhaust waste catalyst |
| 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 |
| CN115612855A (en) * | 2021-07-14 | 2023-01-17 | 谷育英 | Method for recovering metal platinum from platinum-containing waste catalyst |
| CN113564379A (en) * | 2021-07-26 | 2021-10-29 | 福建有道贵金属材料科技有限公司 | Method for recovering precious metal from spent automobile catalyst |
| CN114231749A (en) * | 2021-12-28 | 2022-03-25 | 金川集团股份有限公司 | Method for recovering platinum and rhodium from platinum and rhodium-containing waste liquid |
| CN114231749B (en) * | 2021-12-28 | 2023-11-21 | 金川集团股份有限公司 | Method for recovering platinum and rhodium from platinum and rhodium-containing waste liquid |
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