CN104831073B - A kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts - Google Patents
A kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts Download PDFInfo
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Abstract
A kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts, it is characterized in that: the described technique reclaiming platinum, palladium, rhodium from spent auto-catalysts is as follows: first carry out pretreatment, after be enriched with, carry out remove impurity afterwards, refine is separated, it is thus achieved that the product of relevant platinum, palladium, rhodium after remove impurity；Its good effect is: from pretreatment to being enriched to separation refine and the product output of platinum, palladium, rhodium, whole workflow environment protects, and technique connecting is good, and flow process is simple, and platinum, palladium, rhodium separating-purifying efficiency is high, during platinum direct yield 91%, palladium direct yield 95%.
Description
Technical field
The invention belongs to metal material extractive technique field, the technique particularly relating to reclaim platinum, palladium, rhodium from spent auto-catalysts.
Background technology
Platinum, palladium, 3 elements of rhodium (hereinafter referred to as platinum group metal) have the physicochemical characteristics of uniqueness because of it, have a wide range of applications in Aeronautics and Astronautics, navigation, guided missile, rocket, atomic energy, microelectric technique, chemical, petrochemical industry, glass fibre, waste gas purification and metallurgical industry every field, become modern industry, military project and new high-tech industry important materials, have the title of " modern industry vitamin ".
In recent years, China's platinum group metal consumption figure maintains sustained and rapid growth, and is increased to current tens ton by former several tons.But China's platinum group metal mineral products resource is the deficientest, it is chronically at the state that need to meet demand by import.Along with the development of China's economy science and technology, demand and the import volume of platinum group metal will persistently be risen by China.The platinum group metal product of substantial amounts, after using and losing efficacy, will produce substantial amounts of platinum group metal secondary resource, reclaim platinum group metal, the wretched insufficiency making up China's platinum group metal mineral products resource is had highly important strategic importance from these secondary resources.
Automobile spent catalyst is important platinum group metal secondary resource, it has been reported that 2014 or produced spent auto-catalysts 5000 tons, platinum, palladium, rhodium content is more than 6 tons, and how efficient recovery platinum group metal therein has obtained the extensive concern of insider.
Traditional handicraft main method is to raw material process potassium cloride, it is thus achieved that the content of leached mud platinum, palladium, rhodium about 100-300g/t, and leached mud, again by wet method or thermal process, extracts platinum group metal therein further.The platinum, palladium, rhodium mixed liquor obtained, thioether 30%S201+20% diethylbenzene+50% n-dodecane oil extractant can be used to extract Pd, palladium sponge finally it is reduced into after strip liquor refine, TBP extracts Pt, obtaining spongy platinum after strip liquor refine, the rhodium solution remove impurity of the not platiniferous palladium finally obtained purifies post-treatment and becomes Related product.This process route is the most ripe, effectively can extract platinum, palladium, rhodium from spent auto-catalysts to separate with realizing platinum, palladium, rhodium, direct yield, the response rate and product purity are attained by good result, but also exist that platinum group metal primary recovery is low, extract process many, extraction and the deficiency such as refining process complicated and time consumption, cause that whole return period is longer, reagent consumes big and cost of labor cost is high, production line investment height.
Increasingly competitive along with spent auto-catalysts market, cost of material is more and more higher, use traditional handicraft to reclaim platinum, palladium, rhodium and can not obtain preferable economic benefit, many domestic enterprises are often inferior to other developed country in raw material competition, cause important national strategy resource platinum group metal to be run off external.The competition of raw material has had been transferred to the competition of science and technology, and research environment protects, the response rate high, platinum group metal new recovering technology short, low cost return period becomes one of the most popular research topic.
The most relatively advanced beneficiation technologies is plasma heating furnace pyrometallurgical smelting beneficiation technologies, and isolation technics is molecular recognition technology.The advantage of plasma heating furnace is that the response rate is high, and processing speed is fast, but puts into big, high material consumption；Molecular recognition technology is applied on platinum, palladium, rhodium separates, and can replace traditional abstraction technique, make platinum, palladium, rhodium realize high efficiency separation.
To this end, to overcome above-mentioned deficiency, 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 disadvantages described above, a kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts of the present invention provides the benefit that: effectively solve spent auto-catalysts wet processing leaching rate low, leached mud content is high, the problem that need to extract further, production cost is greatly lowered and improves organic efficiency；Avoid the problem that tradition sodium nitrite complexometry produces a large amount of serious environment pollution nitrogen oxides；The platinum palladium solution obtained after heavy rhodium uses ammonia ammonium chloride jointly to act on, and makes platinum palladium realize good separation, and production efficiency is high, and direct yield is high；Platinum, palladium, rhodium separates the technique concurrently separating platinum palladium after using first separate rhodium, platinum, palladium, rhodium purification process almost can be carried 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.
A kind of technique reclaiming platinum, palladium, rhodium from spent auto-catalysts, it is characterised 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 pretreatment, after be enriched with, carry out remove impurity afterwards, separate refine after remove impurity, it is thus achieved that the product of relevant platinum, palladium, rhodium.
(1) pretreatment
Spent auto-catalysts is size-reduced to sieve, and crossing grit number is more than 200 mesh, and oversize returns and continues grinding and sieving, and siftage carries out sulphuric acid acid etching, and sulphuric acid acid etching temperature is 200-300 DEG C, and sulfuric acid concentration is the acid etching material that 50-98% obtains, and is used for being enriched with operation；
The process that pulverizes and sieves passes through blower fan convulsion and bag collection, and in acid corrosion process, equipment is airtight, and the gas of generation enters 3 grades of absorptions by convulsion, and first 2 grades is water absorbing liquid, and the third level is 20% sodium hydroxide absorbing liquid, and the acid water absorbing liquid of generation returns acid etching and uses；
(2) enrichment
Acid etching material carries out secondary potassium cloride, and leachate 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, 2-4 hour time,
Iron replacement: temperature 40-70 DEG C, acidity 2-6mol/L, displacement terminal is as the criterion with detection equal below the 0.0005g/L of Pt, Pd, Rh content；
Aluminium powder is replaced: temperature 20-50 DEG C, acidity 2-6mol/L, and displacement terminal is as the criterion with detection equal below the 0.0005g/L of Pt, Pd, Rh content；
(3) remove impurity
Replacement slag is through dissolving after liquid making, through cationic resin removal of impurity metal cation, it is thus achieved that remove impurity liquid for next step separating-purifying, insoluble slag returns liquid making and dissolves:
Dissolving liquid making uses hydrochloric acid+oxidant to dissolve: salt acidacidity 8-10mol/L, temperature 70-90 DEG C, oxidation-reduction potential 700-900mV, dissolution time 2-4 hour；
Cation exchange resin regenerated liquid uses hydrochloric acid solution, and acidity 6-10mol/L, after regeneration, cation exchange resin is reusable, and regenerated liquid is replaced, and replacement slag is uniformly processed；
(4) separating-purifying
Heavy rhodium after remove impurity liquid is concentrated, heavy rhodium uses organic sulfur compound to carry out selectivity to sink rhodium, i.e. concentrated solution and control appropraite condition and directly carry out heavy rhodium, first realize the separation of rhodium, and rhodium precipitation can obtain relevant rhodium product after simple refine；
After heavy rhodium, liquid is by adding ammonium chloride and ammonia complexation, and ammonium chloride addition is 0.1-1 times of platinum, and ammonia addition is as the criterion to control pH value of solution 6-8, and palladium generates solubility dichloro four ammino Asia palladium, and platinum generates ammonium chloroplatinate precipitate, it is achieved the separation of platinum palladium；Palladium carries out refine by tradition ammonia complexation hydrochloric acid acidization, repeatedly for three times, is finally reduced into palladium sponge；Platinum carries out refine by tradition ammonium chloroplatinate repeated precipitation process, repeatedly for three times, 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 good effect is: from pretreatment to separation refine and the product output being 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, during platinum direct yield 91%, palladium direct yield 95%.
Accompanying drawing explanation
A kind of process chart reclaiming platinum, palladium, rhodium from spent auto-catalysts of Fig. 1.
Fig. 2 pretreating process flow chart.
Fig. 3 process of enriching flow chart.
Fig. 4 impurity removing process figure.
Fig. 5 platinum, palladium, rhodium process for separating and purifying flow chart.
Detailed description of the invention
Embodiment one:
(1) pretreatment
Spent auto-catalysts is size-reduced to sieve, and crossing grit number is 205 mesh, and oversize returns and continues grinding and sieving, and siftage carries out sulphuric acid acid etching, and sulphuric acid acid etching temperature is 250 DEG C, and sulfuric acid concentration is the 65% acid etching material obtained, and is used for being enriched with operation；
The process that pulverizes and sieves passes through blower fan convulsion and bag collection, and in acid corrosion process, equipment is airtight, and the gas of generation enters 3 grades of absorptions by convulsion, and first 2 grades is water absorbing liquid, and the third level is 20% sodium hydroxide absorbing liquid, and the acid water absorbing liquid of generation returns acid etching and uses；
(2) enrichment
Acid etching material carries out secondary potassium cloride, and leachate 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 with detection 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 with detection Pt, Pd, Rh content for 0.0004g/L；
(3) remove impurity
Replacement slag is through dissolving after liquid making, through cationic resin removal of impurity metal cation, it is thus achieved that remove impurity liquid for next step separating-purifying, insoluble slag returns liquid making and dissolves:
Dissolving liquid making uses hydrochloric acid+oxidant to dissolve；Salt acidacidity 9mol/L, temperature 80 DEG C, oxidation-reduction potential 750mV, dissolution time 3 hours；
Cation exchange resin regenerated liquid uses hydrochloric acid solution, and acidity 8mol/L, after regeneration, cation exchange resin is reusable, and regenerated liquid is replaced, and replacement slag is uniformly processed；
(4) separating-purifying
Heavy rhodium after remove impurity liquid is concentrated, heavy rhodium uses many sulfur organics to carry out selectivity to sink rhodium, and rhodium content 3g/L in solution, acidity 6mol/L, temperature 60 C carries out heavy rhodium, first realizes the separation of rhodium, and rhodium precipitation obtains rhodium product after simple refine；
After heavy rhodium, liquid is by adding ammonium chloride and ammonia complexation, and ammonium chloride addition is 0.5 times of platinum, and ammonia addition is as the criterion to control pH value of solution 7, and palladium generates solubility dichloro four ammino Asia palladium, and platinum generates ammonium chloroplatinate precipitate, it is achieved the separation of platinum palladium；Palladium carries out refine by tradition ammonia complexation hydrochloric acid acidization, repeatedly for three times, is finally reduced into palladium sponge；Platinum carries out refine by tradition ammonium chloroplatinate repeated precipitation process, repeatedly for three times, is finally reduced into spongy platinum；Platinum palladium refining slag returns liquid making system.
Claims (1)
1. the technique reclaiming platinum, palladium, rhodium from spent auto-catalysts, it is characterised in that: the described technique reclaiming platinum, palladium, rhodium from spent auto-catalysts is as follows:
(1) pretreatment
Spent auto-catalysts uses and pulverizes and sieves, and crossing grit number is more than 200 mesh, for the first time after pulverization process, oversize returns, and continues grinding and sieving, and siftage carries out sulphuric acid acid etching, sulphuric 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 convulsion and bag collection, in acid corrosion process, equipment is airtight, and the gas of generation enters 3 grades of tail gas absorbing systems by convulsion, and first 2 grades is water absorbing liquid, the third level is 20% sodium hydroxide absorbing liquid, and the acid water absorbing liquid of generation returns acid etching and uses；
(2) enrichment
Acid etching material carries out secondary potassium cloride, and leachate displacement uses iron replacement or the displacement of aluminum 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, 2-4 hour time；
Iron replacement: temperature 40-70 DEG C, acidity 2-6mol/L, displacement terminal is as the criterion with detection equal below the 0.0005g/L of Pt, Pd, Rh content；
Aluminium powder is replaced: temperature 20-50 DEG C, acidity 2-6mol/L, and displacement terminal is as the criterion with detection equal below the 0.0005g/L of Pt, Pd, Rh content；
(3) remove impurity
Replacement slag impurity cationic after dissolving liquid making, in cation exchange resin removes solution, it is thus achieved that the purest noble metal remove impurity liquid, for next step separating-purifying, insoluble slag returns liquid making and dissolves；
Dissolving liquid making uses hydrochloric acid+oxidant to dissolve；Salt acidacidity 8-10mol/L, temperature 70-90 DEG C, oxidation-reduction potential 700-900mV, dissolution time 2-4 hour；
Cation exchange resin regenerated liquid uses hydrochloric acid solution, and acidity 6-10mol/L, after regeneration, cation exchange resin is recycling, and regenerated liquid is replaced, and replacement slag is uniformly processed；
(4) separating-purifying
Remove impurity liquid is heavy rhodium after concentrating, and heavy rhodium uses 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, and temperature 40-90 DEG C carries out heavy rhodium, first realizes the separation of rhodium, and rhodium precipitation can obtain rhodium product after simple refine；
After heavy rhodium, liquid is by adding ammonium chloride and ammonia complexation, and ammonium chloride addition is 0.1-1 times of platinum, and ammonia addition is as the criterion to control pH value of solution 6-8, and palladium generates solubility dichloro four ammino Asia palladium, and platinum generates ammonium chloroplatinate precipitate, it is achieved the separation of platinum palladium；Palladium carries out refine by tradition ammonia complexation hydrochloric acid acidization, repeatedly for three times, is finally reduced into palladium sponge；Platinum carries out refine by tradition ammonium chloroplatinate repeated precipitation process, repeatedly for three times, is finally reduced into spongy platinum；Platinum palladium refining slag returns liquid making system.
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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 |
| 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 |
| CN106367611B (en) * | 2016-09-13 | 2018-03-30 | 中南大学 | It is a kind of from useless Pd/Al2O3The method of separating enriched palladium in catalyst chloridizing leach solution |
| CN107574303A (en) * | 2016-11-21 | 2018-01-12 | 广西大学 | A kind of method of hydrazine hydrate reduction automobile spent catalyst |
| 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 |
| CN110016555B (en) * | 2019-05-14 | 2021-01-05 | 贵研资源（易门）有限公司 | Method for separating and purifying noble metal 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 |
| CN112029998B (en) * | 2020-08-27 | 2022-03-18 | 湖南高鑫铂业有限公司 | 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 |
| 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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