CN1458291A

CN1458291A - Noble metalregeneration recovering method for electronic waste material

Info

Publication number: CN1458291A
Application number: CN03137220A
Authority: CN
Inventors: 姚洪; 王洪涛; 傅昌荣; 林桂燕; 裘忠富; 沈强; 李广安; 胡国良
Original assignee: ZHEJIANG PROV METALLURGY INST CO Ltd
Current assignee: ZHEJIANG PROV METALLURGY INST CO Ltd
Priority date: 2003-06-02
Filing date: 2003-06-02
Publication date: 2003-11-26
Anticipated expiration: 2023-06-02
Also published as: CN1208479C

Abstract

The noble metal regenerating and recovering method from electronic waste material includes pre-treatment of grinding, magnetically selecting and sieving to obtain noble metal containing powder; oxidation to loeaching through adding hydrochloric acid and complexing agent, dropping hydrogen peroxide while heating, leaching for at least 1.5 hr, eliminating superntant to obtain leaches liquid; adding iron powder into the leached liquid to obtain noble metal sludge via replacement; extracting from nobile metal sludge through leaching noble metal sludge, complex salt deposition, adding oxidant until producing chlorine and obtaining complex salt deposit; and purifying Pd. The present invention has the advantages of advanced technological process, low cost and high efficiency.

Description

The precious metal regeneration recovery method of electronic waste

Technical field

What the present invention relates to is that a kind of precious metal waste that contains to low levels is regenerated and reclaimed the method for precious metal, especially a kind of method that the precious metal regeneration of useless electronics material is reclaimed.

Background technology

Precious metal, especially platinum family precious metal, it has unique physics and chemical property, is widely used in every field such as military project, oil, chemical industry, organic synthesis, microelectronics, tail gas clean-up, plays irreplaceable effect in Modern High-Tech's industry.In the platinum family precious metal, the use of platinum, palladium is the most extensive, and output is extremely low, and according to statistics, the now annual output in the whole world is less than 200 tons, and the annual production of China is 1 ton of less than especially.For these precious metal ores, belonged to rich ore if can reach gram/tonne content, have commercial mining and be worth.But contain in the waste of precious metal at some, the content of precious metal but can reach nearly a few hectogram/ton, as the electronic component etc. that gives up, some in addition more, therefore to the regeneration of the waste that contains precious metal, the problem for solving China's precious metal resource famine has crucial meaning.At present, China is to from the high-load waste that contains precious metal, reclaim precious metal in the catalyzer of scrapping as industries such as medicine, petrochemical industry, existing sophisticated recovery technology, and for low levels to contain the technology that the precious metal waste reclaims also far immature, be in conceptual phase, chief reason is that the waste of these low content of noble metal just begins to produce gradually in recent years, and the bullion content of these wastes is low, composition is comparatively complicated, and the technical requirements of reclaiming is higher relatively.

Summary of the invention

The object of the present invention is to provide a kind of precious metal regeneration recovery method that from useless electronic component, reclaims electronic waste precious metal, that reach low cost, high-level efficiency, low pollution requirement, four big operations such as it comprises that the pre-treatment of useless electronic component, oxidation are leached, filtrate displacement and your mud essence are carried, wherein: a, pre-treatment: the electronic component pulverize that will give up obtains containing the precious metal powder through the magnetic separation screening; B, oxidation are leached: add hydrochloric acid, complexing agent in the container that the precious metal powder is housed successively, be not less than in heating under 40 ℃ the condition, leached through at least 1.5 hours after dripping hydrogen peroxide, take out supernatant liquor and obtain leach liquor, wherein added component concentration is determined by following condition: water: hydrochloric acid≤3: 1, liquid: Gu 〉=4: 1, hydrogen peroxide: Gu 〉=1: 3, complexing agent: Gu 〉=1: 10; C, filtrate displacement: add iron powder in above-mentioned leach liquor, your mud the displacement through at least three hours obtains; D, your mud essence are carried: carry out your mud earlier and leach, be not less than under 60 ℃ of temperature, press liquid: Gu 〉=4: 1, water: hydrochloric acid≤1: 1, sodium chlorate: Gu 〉=1: 10, condition, add hydrochloric acid and sodium chlorate and carry out your mud leaching, and carry out once at least, then, carry out double salt precipitation, in your mud leach liquor, add NH4Cl, and the NH4Cl concentration in the assurance mixed solution adds oxygenant again more than 10%, obtains double salt precipitation after producing chlorine; Carries out the purification of palladium again, in above-mentioned double salt, add ammoniacal liquor, and control PH is about 9, obtain filtrate after, with analytical pure hcl acidifying solution to PH about 1.5, obtain the complex salt precipitation, through the washing reduction, obtain pure palladium sponge again.

In the described preprocessing process, after screening, will be used for oxidation and leach, pulverize, and sieve again and obtain being used for oxidation and leach less than 40 purpose parts material and will after impurity is removed in magnetic separation, send into wet ball-milling again greater than 40 purpose powders less than 40 purpose powders.

Describedly will carry out oxidation less than 40 purpose powders and leach, and after taking out supernatant liquor, the leached mud that stays is carried out the leaching of a same processes and extracts supernatant liquor getting leach liquor again, wherein the condition of Jin Chuing is: water: acid 〉=5: 1, liquid: Gu 〉=4: 1, hydrogen peroxide: Gu 〉=1: 6, complexing agent: Gu 〉=3: 50.

Described your mud carries out the double salt precipitation operation after leaching and carrying out three times at least again.

The present invention by useless electronic component is pulverized, is leached, displacement, complexing leaching, double salt precipitation, your mud essence mention operations such as thick palladium purification, through obtaining after the pilot scale: in the useless electronic component of 35 tons of low precious metal contents, reclaim palladium sponge 28180 grams, spongy platinum 5200 grams, gold 150 grams, the rate of recovery of platinum and palladium reaches 97.4% and 96.5% respectively, dna purity can reach more than 99.95%, has the technology advanced person, and cost is low, characteristics such as efficient height have tangible economic and social benefit.

Embodiment

Below with the present invention will be described in detail:

The present invention mainly includes pre-treatment, oxidation leaching, leach liquor displacement and your mud essence and four big operations such as puies forward.1, pre-treatment: choose the useless electronic component of 20Kg, behind wet ball-milling, make powder-material, contain the precious metal powder by sieving, filtering out less than 40 purposes, greater than 40 powder materials through iron removal by magnetic separation, other powder carries out wet ball-milling again, and screening contains the precious metal powder after leaching less than 40 purposes, generally can obtain iron content leftover bits and pieces pin material 3.86kg, contain precious metal powder 16.14kg, this contains the precious metal powder and is used for next process.

2, oxidation is leached: leach acidity, i.e. water for the first time: hydrochloric acid=3: 1, leach concentration, be liquid: Gu=4: 1, hydrogen peroxide: Gu=1: 3, complexing agent: Gu 〉=condition such as 1: 10, get 250g and contain the precious metal powder and put into container, add certain density hydrochloric acid soln by above-mentioned liquid-solid ratio condition, add complexing agent, be heated to 40 ℃, drip hydrogen peroxide and leach, after 1.5 hours, leach and finish, add the sodium sulfate deleading of 10g again.

In the condition that above-mentioned oxidation is leached, it is high more to leach acidity, and its leaching yield is also high more, but has arrived certain acidity, and the leaching yield ascendant trend is slowed down, and is good with 3: 1; Equally, reduce to leach concentration, promptly liquid-solid ratio helps the leaching of precious metal, but can increase reagent cost and facility investment simultaneously, therefore, with above-mentioned be chosen as good.The hydrogen peroxide quantity not sufficient, the just base metal of leaching, have only hydrogen peroxide arrive a certain amount of after, precious metal could leach, present embodiment adding hydrogen peroxide 100ml.Equally, add the leaching that complexing agent helps precious metal, generally adding the 25g complexing agent under these conditions can meet the demands.

The oxidation of carrying out is under these conditions leached, general leaching yield for improving leaching yield, can be selected to carry out the second time and oxidation for the third time and leach about 90%, they are that the preceding supernatant liquor that once leaches is extracted out, stay leached mud, add an amount of water and acid simultaneously, begin then to stir, drip hydrogen peroxide behind certain hour, stop to stir, extract supernatant liquor, soak the solution that slag adds certain acidity again and begin to leach for the third time.Because the back secondary leaches, its base metal that stays seldom exists, and therefore, acidity can suitably be hanged down, the hydrogen peroxide consumption also can reduce, so the selection condition that back secondary leaches is: leaching acidity is water: hydrochloric acid=5: 1, leach concentration, be liquid: Gu=4: 1, extraction time needed 1 hour to get final product hydrogen peroxide consumption 50ml, complexing agent consumption: 15g.

3, leach liquor displacement: owing to contain a large amount of base metals in the above-mentioned leach liquor, precious metal ion concentration is extremely low simultaneously, therefore adds iron powder in leach liquor, and your mud displacement obtains, and copper content is high in your mud, accounts for more than 50% bullion content about about 2%.

4, the precious metal essence is carried: it comprises purification of your mud leaching, double salt precipitation, palladium etc.Wherein to leach be to adopt efficiently that acid solution adds sodium chlorate for your mud, and its leaching condition is: 65 ℃ of extraction temperatures, leach concentration, i.e. liquid: Gu=4: 1; Leach acidity, i.e. water: hydrochloric acid=1: 1; Sodium-chlor: Gu=1: 10, about 1.5 hours of extraction time, above-described your mud leaches can be carried out three times continuously, and its leaching yield is reached more than 98%.

Add ammonia chloride again in the leach liquor after your mud leaches and oxygenant carries out double salt precipitation, get 4: 1 leach liquor 500ml in container, be heated to about 50C, add a certain amount of solid ammonia chloride then, stirring makes it dissolving, and guarantees the concentration more than 10%, and second edition adds oxygenant, constantly stir, until producing red foam layer.In throw out, add ammoniacal liquor, about control PH=9, make Cu, Pd dissolving metal in solution, and base metal hydrates such as Pb, Sn, Fe are removed, by the above solution that obtains, transfer to about PH=1.5 with analytical pure hcl acidifying solution, make Pd become the complex salt precipitation, copper is stayed in the solution, the washing complex salt can obtain more purified Pd salt, reduction Pd salt just can obtain palladium sponge.

Claims

The precious metal of 1 one kinds of electronic wastes regeneration recovery method, it is characterized in that it mainly by pre-treatment, oxidation leach, filtrate displacement and your mud essence put forward four big operations and form, wherein:

A, pre-treatment: the electronic component pulverize that will give up obtains containing the precious metal powder through the magnetic separation screening;

B, oxidation are leached: add hydrochloric acid soln, complexing agent in the container that the precious metal powder is housed successively, be not less than in temperature under 40 ℃ the condition, drip behind the hydrogen peroxide through agitation leach at least 1.5 hours, take out supernatant liquor and obtain leach liquor, wherein added component concentration is determined by following condition: water: hydrochloric acid≤3: 1, liquid: Gu 〉=4: 1, hydrogen peroxide: Gu 〉=1: 3, complexing agent: Gu 〉=1: 10;

C, filtrate displacement: add iron powder in above-mentioned leach liquor, your mud the iron replacement through at least three hours obtains;

D, your mud essence are carried: carry out your mud earlier and leach, be not less than under 60 ℃ of temperature, press liquid: Gu 〉=4: 1, water: hydrochloric acid " 1: 1, sodium chlorate: Gu 〉=1: 10, condition, add hydrochloric acid and sodium chlorate and carry out your mud and leach, and carry out once at least, then, carry out double salt precipitation; In your mud leach liquor, add NH4Cl, and guarantee that NH4CL concentration in the mixed solution more than 10%, adds oxygenant again, after producing chlorine, obtain double salt; Precipitation is carried out the purification of palladium again, adds ammoniacal liquor in above-mentioned double salt, and control PH is about 9, obtain filtrate after, with analytical pure hcl acidifying solution to PH about 1.5, obtain the complex salt precipitation, through the washing reduction, obtain pure palladium sponge again.
2, the precious metal of electronic waste according to claim 1 regeneration recovery method, it is characterized in that in the described preprocessing process, to be used for oxidation less than 40 purpose powders after screening leaches, pulverize and will after impurity is removed in magnetic separation, send into wet ball-milling again, sieve again and obtain being used for oxidation and leach less than 40 purpose parts material greater than 40 purpose powders.
3, the precious metal of electronic waste according to claim 2 regeneration recovery method, it is characterized in that describedly will carrying out oxidation less than 40 purpose powders and leaching, and after taking out supernatant liquor, the leached mud that stays is carried out the leaching of a same processes and extracts supernatant liquor getting leach liquor again, wherein the condition of Jin Chuing is: water: acid 〉=5: 1, liquid: Gu 〉=4: 1, hydrogen peroxide: Gu 〉=1: 6, complexing agent: Gu 〉=3: 50.
4, the precious metal of electronic waste according to claim 1 regeneration recovery method is characterized in that carrying out the double salt precipitation operation again after described your mud leaching is carried out leaching for three times at least.