CN105018733B - The enrichment of bismuth element and separation method in many metal mixed resources of waste printed circuit board - Google Patents
The enrichment of bismuth element and separation method in many metal mixed resources of waste printed circuit board Download PDFInfo
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- CN105018733B CN105018733B CN201510402138.9A CN201510402138A CN105018733B CN 105018733 B CN105018733 B CN 105018733B CN 201510402138 A CN201510402138 A CN 201510402138A CN 105018733 B CN105018733 B CN 105018733B
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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
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Abstract
The enrichment of bismuth element and separation method in cycling and reutilization technology, specially a kind of many metal mixed resources of waste printed circuit board are integrated the invention belongs to complicated non-ferrous metal secondary resource.First, waste printed circuit board obtains the multi-metal complex mixture containing bismuth element after broken+sorting, release agent is added in multi-metal complex mixture, the multi-metal complex mixture configured is placed in the graphite crucible of vacuum drying oven, after metal mixture is completely melt, add trapping agent lead, then micro pregnant solution is added, bismuth element selective enrichment is into lead liquid phase, stratified liquid occurs for the melt in crucible, the separation melt that upper strata is liquid copper and lower floor is liquid lead is formed, upper strata liquid copper and the lower floor's liquid lead for having trapped bismuth element are mutually poured out respectively.Thus, bismuth is separated from waste printed circuit board multi-metal complex mixture, and is recycled.The present invention is simple and easy, with cost is low, comprehensive high-efficiency, it is pollution-free the features such as.
Description
Technical field
Cycling and reutilization technology, specially a kind of waste printed circuit board are integrated the invention belongs to complicated non-ferrous metal secondary resource
The enrichment of bismuth element and separation method in many metal mixed resources, are related in environmental protection technical field and electron wastes are carried out
Reclaim, regenerate and comprehensive high-efficiency resource technology, help and solve the problems, such as electron wastes to the harm of ecological environment and alleviate me
The pressure of state's non-ferrous metal shortage of resources.
Background technology
With the update constantly brought forth new ideas with electric equipment products of science and technology, a large amount of waste electric products have turned into
Growth rate most fast and most intractable class solid waste.Electron wastes are also known as electronic waste, including various waste and old electricity
Brain, communication equipment, household electrical appliance and precision electronic device instrument for being eliminated etc..According to statistics, every thousand people is put down in the whole world in 2002
Computer owning amount is about 100, and has ever-increasing trend.The social recoverable amount of domestic television machine in 2010 is more than 3.7
Hundred million, computer, refrigerator and washing machine are respectively more than 80,000,000,1.5 hundred million and 1.9 hundred million.In general, refrigerator, wash
The average life of clothing machine in 8 to 10 years, television set average life in 4 to 6 years, as the faster computer that updates
The superseded cycle with mobile phone, especially mobile phone was even shorter in 1 to 3 year.Estimate according to United Nations Environment Programme, the whole world is often produced per year
Raw about 4000~60,000,000 tons of electronic wastes, wherein US and European accounts for 1/3 and 1/4 respectively.China is only second to the U.S.
Second largest electron wastes producing country.In addition, external electronic waste continually pours into China.It is reported that the whole world 90%
" electronic waste " enters Asia, wherein about 80% enters China's Mainland.In all kinds of electron wastes, wherein waste printed circuit board
Averagely account for the 4% of total amount.However, being eliminated or the electronic product such as tablet personal computer, notebook computer, mobile phone that turnover rate is high
In, circuit board proportion is up to 40%.
As the important composition part of electron wastes, waste printed circuit board (WCB) but contains substantial amounts of metals resources, gold
Category accounts for the 40% of circuit board gross weight.By weight percentage, 0.5 is included in waste printed circuit board multi-metal complex mixture
~6.0% aluminium, 1%~2.5% silicon, 0.1%~1.0% chromium, 0.05%~1.0% manganese, 5.0%~10% iron, 0.05%~
1.0% cobalt, 1.5%~3.0% nickel, 60%~80% bronze medal, 0.5%~1.5% zinc, 0.05%~0.1% silver medal, 0.05%~
1.0% cadmium, 5.0%~8.0% tin, 0.5%~1.0% antimony, 0.05%~0.1% gold medal, 2.0%~5.0% lead, 0.5%~
The metallic elements such as 1.0% bismuth.It can be seen that, the metal contained in waste printed circuit board is tens times or even hundred times of native deposits, it
Be both environmentally hazardous rubbish, be valuable resource again.
The recycling technology of metals resources is broadly divided into mechanical-physical processing, hydrometallurgy, biology in waste printed circuit board
Metallurgy, pyrometallurgy etc. or several treatment technologies are combined：
1. mechanical-physical processing (《The process for breaking, separating and recovering and its device therefor of printed circuit board (PCB)》, referring to middle promulgated by the State Council
Bright patent (patent 99102862.7, publication number CN1238244A)；《The broken and high-pressure electrostatic separation method of waste and old circuit board》,
Referring to Chinese invention patent (patent No. 200510023785.5, publication number CN1313208A)；《Metal enrichment in waste printed circuit board
The physiochemical mutagens technique of body》, referring to Chinese invention patent (patent No. 200410014582.5, publication number CN1563440A)).Should
Method is that discarded circuit board first is ground into particle using plant equipment, then recycles each component physical property (such as：Density, conduction
Property etc.) difference, realize metal and nonmetallic separation.Using mechanical-physical facture, more than 95% gold in waste printed circuit board
Category material can be recycled.But, the metal of separation is the complicated secondary metals resource that Determination of multiple metal elements is mixed,
Many metal mixtures must be separated and cycling and reutilization, metals resources could be realized.
2. hydrometallurgy (《The method for separating and recovering valuable metal in many metal enrichment powder of waste printed circuit board》, referring to China
Patent of invention (patent No. 201210267821.2, publication number CN102747229A)；《A kind of discarded circuit of Selectively leaching separation
The method of tin, lead and copper in plate》, referring to Chinese invention patent (patent No. 200910082443.9, publication number
CN101864519A)).This method is that waste printed circuit board is placed in strong acid solution, and metallics occurs chemical reaction and dissolved,
Then metallic element is reclaimed from solution.However, this method is low to the leaching efficiencies of part metals, act on limited, especially by
The metallic element being wrapped in ceramics can not be reclaimed；The technology especially weak point is that chemical reagent consumption amount is big, is produced simultaneously
It is a large amount of to contain waste liquid and the waste residue being corrosive with toxicity and heavy metal ion, easily cause secondary pollution.
3. biological metallurgy (《The waste printed circuit board method for recovering precious metals of joint physical separation and Bioleaching》, in
State's application for a patent for invention (application number 201310262065.9, publication number CN103320618A)；《Copper reclaims system in waste printed circuit board
System》, referring to Chinese utility model patent (patent No. 201220074426.8, publication number CN202519343U)；《Biological wet method smelting
Technology for gold reclaims the progress of valuable metal in discarded circuit board》, non-ferrous metal scientific and engineering, 1 phase in 2013).The skill
Art is to be interacted using certain microorganism or its metabolite with the metallic element in waste printed circuit board, produce oxidation, reduction,
The reactions such as absorption, dissolving, so that the recovery of metallic element in waste printed circuit board is realized, but it is limited due to being currently known strain, and
Industrialization amplification culture is difficult, the leaching velocity of metal is slower, and the production cycle of removal process is long, low production efficiency.
4. pyrometallurgy.The technology is to be heated at high temperature waste printed circuit board under oxygen-enriched environment by smelting furnace, peels off non-gold
Belong to material, and the metallics melted flows out in alloy melt, then reclaim metallic element, but right and wrong by refining and being electrolysed processing
Metallics can produce volume of smoke or toxic gas in combustion, have harm to air ecological environment.
As can be seen here, during recycling treatment waste printed circuit board metallic element, prior art also exist limitation or
It is not enough.Although developed during electron wastes are disassembled sealing-off technology (referring to《Circuit board element and solder separation and recovery
Method and device》, Chinese invention patent, the patent No. CN200710201532.1, publication number CN101112728).But, at present
Rational enrichment, separation and recycling method are not proposed to bismuth element in many metal mixtures of waste printed circuit board.Bismuth
It is widely used in metallurgy, chemical industry, electronics, aerospace, medicine and other fields.Comparatively, bismuth member in many metal mixtures of waste printed circuit board
Plain grade is higher by the decades of times of natural crystal.Therefore, in many metal mixtures of waste printed circuit board of the present invention the enrichment of bismuth element with
Separation method, contributes to the pressure saved nonferrous metal resource and alleviate China's nonferrous metal resource shortage.
The content of the invention
It is an object of the invention to overcome prior art not enough there is provided a kind for the treatment of by stages, simple and direct technique, high efficiency,
The enrichment of bismuth element and separation method in low emission, many metal mixed resources of environmentally friendly waste printed circuit board, by bismuth element from
Separated in hybrid metal, realize the recovery to bismuth metal in waste printed circuit board and recycling treatment.
In order to realize this purpose, present invention utilizes the metallurgy feature and metallic element of metal liquid-liquid separation in liquid
Selectivity distribution behavior and its control technology in phase-separation system, the trace element and use different by adding are different
Technological parameter, apportionment ratio of the regulation and control metallic element in liquid-phase separating system makes the Biosorption of Metal Elements that is recovered and is fixed on
In predetermined liquid phase, separated so as to realize and be recovered metallic element from many metal mixtures of waste printed circuit board, final
With green reclaim and cycling and reutilization.
For the separation of bismuth element in many metal mixtures of waste printed circuit board, first, waste printed circuit board is after broken+sorting
The multi-metal complex mixture containing bismuth element is obtained, release agent, trapping agent, enrichment are added in multi-metal complex mixture
Agent, the metal mixture prepared is placed in heat in the graphite crucible of vacuum furnace and melted, modulation process parameter sends out melt
Raw liquid-liquid separation, metal bismuth element selective enrichment is in lead liquid phase, due to there is density contrast between liquid copper and liquid lead,
Under gravity, stratified liquid occurs for the melt in crucible, forms the separation that upper strata is liquid copper and lower floor is liquid lead and melts
Body.Thus, bismuth element is separated from waste printed circuit board multi-metal complex mixture, and is recycled, and is specifically included
Following steps：
Step 1 carries out broken+sorting to waste printed circuit board, and the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element；
Step 2 adds release agent silicon or aluminium element in multi-metal complex mixture, silicon or aluminium element is matched more golden
The mass fraction for belonging to shared in mixture is 5%~18%, and the multi-metal complex mixture configured is placed in into vacuum furnace
Black-fead crucible in；
After the sealing of step 3 vacuum furnace, start vacuum-pumping system, after vacuum is less than 10Pa, is filled with nitrogen, subtracts
The volatilization of small low-melting-point metal element and metal is avoided to aoxidize；
Step 4 starts vacuum furnace power supply, is heated to 1100~1150 DEG C, treats many metal mixtures in graphite crucible
After being completely melt, mechanical agitation 5 minutes, and it is incubated 5~10min；
Step 5 reduces melt temperature, and adds trapping agent lead element, makes lead element proportioning shared in graphite crucible melt
Mass fraction be 30%~60%, melt liquid-liquid separation is into liquid copper and liquid lead；
Step 6 adds pregnant solution, regulation and control liquid copper and the separation rate of liquid lead two-phase, makes bismuth element selectivity quick rich
Collect in lead liquid phase；
Step 7 reduces melt temperature near liquid copper phase fusing point, liquid copper and liquid lead in mechanical agitation graphite crucible
10~15min of blend melt；
Step 8 keeps melt temperature to stand 10~30min, because there is density contrast between liquid lead and liquid copper, in gravity
Melt in the lower crucible of effect is layered, and the layering melt that upper strata is liquid copper and lower floor is liquid lead is formed, by upper liquid
State copper is poured out, and is continued on for other with the separation of targetedly metallic element and cycling and reutilization；
Then step 9 is poured out the remaining lower floor's liquid lead for having trapped bismuth element in crucible, and detect bismuth in liquid lead
The mass content of element, if bismuth element mass content is less than 5%, liquid lead is returned in step 5 and recycled, as trapping agent
Lead element is used for the enrichment of bismuth element in many metal mixed resources of waste printed circuit board of next batch with separating.
Added in many metal mixed resources of described waste printed circuit board in the enrichment of bismuth element and separation method, step 2
Release agent aluminium element is mainly derived from the aluminum metal that electron wastes are dismantled, and is integrated the metal of electron wastes
Recycle.
In many metal mixed resources of described waste printed circuit board in the enrichment of bismuth element and separation method, step 6, addition
Pregnant solution is mainly alkali metal (such as：Sodium, potassium etc.) oxide.
In many metal mixed resources of described waste printed circuit board in the enrichment of bismuth element and separation method, step 9, pour out
Lower floor's liquid lead of bismuth element has been trapped, 350~450 DEG C are cooled to, a small amount of In Crystal Solid Copper is separated out in melt, then using centrifugation point
From or solid-liquid filtration isolation technics, liquid lead can further be separated with copper, if the bismuth element mass content in liquid lead
Predetermined value has been reached, coloured smelting factory is sent to, metallurgical addition agent or solder are manufactured after refining.Thus, bismuth element is from discarded electricity
Separate, and recycled in the plate multi-metal complex mixture of road.
Advantages of the present invention and beneficial effect are：
1st, the present invention utilizes the metallurgy feature and metallic element of metal itself liquid-liquid separation in liquid-phase separating system
Selectivity distribution behavior and its control technology, the element such as different release agents, trapping agent and pregnant solution and use by adding
Different technological parameters, apportionment ratio of the regulation and control metallic element in liquid-phase separating system, make the Biosorption of Metal Elements that is recovered and
It is fixed in predetermined liquid phase, is separated from each other so as to realize and be recovered metallic element with many metal mixtures of waste printed circuit board, most
Green reclaim and cycling and reutilization are able to eventually.The enrichment of bismuth element is with separating in many metal mixed resources of waste printed circuit board of the present invention
Method is simple and easy to apply, with comprehensive high-efficiency, low cost, it is environment-friendly the features such as；The release agent aluminium element of addition is because derive from
Electron wastes, can make the major metal aluminium of electron wastes obtain comprehensive high-efficiency cycling and reutilization；By the liquid of upper lower leaf
Copper and liquid lead are poured out respectively, and upper strata liquid copper continues on for other with the separation of targetedly metallic element and extraction, trapping
Lower floor's liquid lead of bismuth element can be recycled, and waste printed circuit board many metals of next batch are used for as trapping agent lead element
The separation and extraction of bismuth element in resource are mixed, after the bismuth element mass content in lead liquid reaches predetermined value, coloured smelting is sent to
Refinery, manufactures metallurgical addition agent or solder after refining.Waste printed circuit board is reclaimed with hydrometallurgy and extensive pyrometallurgy etc.
The method of middle valuable metal is compared, the present invention reduce secondary pollution, save the energy in terms of and metals resources comprehensive high-efficiency again
Substantially there is bigger advantage using aspect.
2nd, containing substantial amounts of ferrous metal, non-ferrous metal, rare precious metal etc. in circuit board, waste printed circuit board of the invention is more
The separation of metal mixed resource and recycling method, help efficiently to recycle non-ferrous metal secondary resource, alleviate China
The pressure of nonferrous metal resource shortage, it is ensured that China's sustainable economic development.In addition, many metals of waste printed circuit board of the present invention are mixed
The separation in joint source and recycling method, because its separation process occurs in the vacuum or anaerobic heating furnace, it is to avoid because
Secondary pollution caused by waste gas and discharge of wastewater, the characteristics of possessing environment-friendly.Therefore, how golden waste printed circuit board of the invention be
The separation of category mixing resource has economy and environment double benefit with recycling method.
Embodiment
In a specific embodiment, it is sharp again with circulation the invention provides the separation of waste printed circuit board mixing multiple metallic element
With method, the specifically selectivity using the metallurgy feature and metallic element of metal liquid-liquid separation in liquid-phase separating system
Distribution behavior and its control, by adding, different release agents, trapping agent and pregnant solution element and the different techniques of use are joined
Number, apportionment ratio of the regulation and control metallic element in liquid-phase separating system makes the Biosorption of Metal Elements that is recovered and is fixed on trapping agent
In liquid phase, separated so as to realize and be recovered metallic element from many metal mixtures of waste printed circuit board, be finally able to green
Reclaim and cycling and reutilization.
For bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, waste printed circuit board is broken first
Broken+sorting, the metal in waste printed circuit board is separated from nonmetallic, obtains the multi-metal complex mixing containing bismuth element
Thing.Release agent silicon or aluminium are added in multi-metal complex mixture, matches silicon or aluminium element shared in many metal mixtures
Mass fraction be 5%~18%, the multi-metal complex mixture configured is placed in the black-fead crucible of vacuum furnace.Very
After empty heating furnace sealing, start vacuum-pumping system, nitrogen is then charged with, to reduce the volatilization of low-melting-point metal element and avoid
Metal is aoxidized.Then, start vacuum furnace power supply, be heated to 1100~1150 DEG C, treat many metal mixeds in graphite crucible
After thing is completely melt, mechanical agitation 5 minutes, and it is incubated 5~10min.Melt temperature is reduced to 900~1050 DEG C, and addition is caught
Collect agent lead element, the mass fraction for making lead element proportioning shared in graphite crucible melt is 30%~60%, melt liquid-liquid point
From into liquid copper and liquid lead.Afterwards, micro pregnant solution is added, makes pregnant solution in the mass fraction shared by graphite crucible melt
For 0.5%~3%, regulation and control liquid copper and the separation rate of liquid lead two-phase make the selective fast enriching of bismuth element into lead liquid phase,
Further reduction melt temperature to liquid copper phase fusing point nearby (800~1050 DEG C), in mechanical agitation graphite crucible liquid copper and
Liquid lead blend melt about 10~15min, then keep melt temperature stand 10~30min, between liquid lead and liquid copper because
There is density contrast, the melt in crucible is layered under gravity, form that upper strata is liquid copper and lower floor is liquid lead
Melt is layered, the melt of upper lower leaf is poured out respectively.The upper strata liquid copper poured out, continues on for other with targetedly golden
Belong to element sepatation and cycling and reutilization；In the lower floor's liquid lead for having trapped bismuth element, if the mass content of bismuth element is less than
5%, liquid lead is returned in piece-rate system and recycled, and many metals of waste printed circuit board of next batch are used for as trapping agent lead element
Mix the multi-cycle separation of bismuth element and extraction in resource.Reached or close to after 5% after the bismuth element mass content in lead liquid, no longer
Piece-rate system is returned, coloured smelting factory is sent to, metallurgical addition agent or solder etc. are manufactured after refining.Thus, bismuth element is from discarded
Separated in circuit board multi-metal complex mixture, and be able to cycling and reutilization.
Below, technical scheme is further described by embodiment.
Embodiment 1
In the present embodiment, for bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, it is carried out and tested
The experiment of card property.Broken+sorting is carried out to waste printed circuit board first, the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element.Release agent element silicon is added in multi-metal complex mixture, makes silicon
Element proportioning mass fraction shared in many metal mixtures is 10%, and the multi-metal complex mixture configured is placed in very
In the black-fead crucible of empty heating furnace.Then, vacuum furnace is sealed, starts vacuum-pumping system, works as vacuum<After 10Pa, to
Nitrogen is filled with heating furnace nacelle, to reduce the volatilization of low-melting-point metal element and avoid METAL HEATING PROCESS process from aoxidizing.Start true
Empty heating furnace power supply, is heated to 1100 DEG C, after many metal mixtures in graphite crucible are completely melt, mechanical agitation 5min,
And it is incubated 5min.Then, reduction melt temperature adds trapping agent lead element to 900 DEG C, makes lead element proportioning molten in graphite crucible
Shared mass fraction is 50% in body, and melt liquid-liquid separation is into liquid copper and liquid lead.Melt temperature is kept at 900 DEG C,
Micro pregnant solution sodium oxide molybdena, regulation and control liquid copper and the separation rate of liquid lead two-phase are added in melt, bismuth element selectivity is quick rich
Collect in lead liquid phase.Melt temperature is reduced to 860 DEG C, in mechanical agitation graphite crucible liquid copper with liquid lead blend melt about
10min.In melt temperature, 860 DEG C stand 10min, because there is density contrast between liquid lead and liquid copper, under gravity earthenware
Melt in crucible is layered, and the layering melt that upper strata is liquid copper and lower floor is liquid lead is formed, by the melt of upper lower leaf
Pour out respectively.Thus, bismuth element is separated from many metal mixtures of waste printed circuit board.Upper strata liquid copper continues on for other
With the separation of targetedly metallic element and cycling and reutilization.Chemical analysis results show, after once trapping bismuth element, under
Bismuth element mass content in layer lead liquid has reached 0.07%, and the bismuth element mass content in liquid copper is 0.002%, discards
The most separation and concentrations of bismuth element in many metal mixtures of circuit board are into lead liquid phase.
Embodiment 2
In the present embodiment, for bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, it is carried out and tested
The experiment of card property.Broken+sorting is carried out to waste printed circuit board first, the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element.Release agent element silicon is added in multi-metal complex mixture, makes silicon
Element proportioning mass fraction shared in many metal mixtures is 10%, and the multi-metal complex mixture configured is placed in very
In the black-fead crucible of empty heating furnace.Then, vacuum furnace is sealed, starts vacuum-pumping system, works as vacuum<After 10Pa, to
Nitrogen is filled with heating furnace nacelle, to reduce the volatilization of low-melting-point metal element and avoid METAL HEATING PROCESS process from aoxidizing.Start true
Empty heating furnace power supply, is heated to 1100 DEG C, after many metal mixtures in graphite crucible are completely melt, mechanical agitation 5min,
And it is incubated 10min.Then, reduction melt temperature adds trapping agent lead element to 900 DEG C, makes lead element proportioning in graphite crucible
Shared mass fraction is 50% in melt, and melt liquid-liquid separation is into liquid copper and liquid lead.Melt temperature is reduced to 830 DEG C,
Micro pregnant solution sodium oxide molybdena, regulation and control liquid copper and the separation rate of liquid lead two-phase are added in the melt, and bismuth element is selectively quick
It is enriched in lead liquid phase.Keep 830 DEG C of melt temperature, in mechanical agitation graphite crucible liquid copper with liquid lead blend melt about
15min.In melt temperature, 830 DEG C stand 30min, because there is density contrast between liquid lead and liquid copper, under gravity earthenware
Melt in crucible is layered, and the layering melt that upper strata is liquid copper and lower floor is liquid lead is formed, by the melt of upper lower leaf
Pour out respectively.Thus, bismuth element is separated from many metal mixtures of waste printed circuit board.Upper strata liquid copper continues on for other
With the separation of targetedly metallic element and cycling and reutilization.Chemical analysis results show, after once trapping bismuth element, under
Bismuth element mass content in layer lead liquid has reached 0.081%, and the bismuth element mass content in liquid copper is 0.002%, gives up
The most separation and concentrations of bismuth element abandoned in many metal mixtures of circuit board are into lead liquid phase.
Embodiment 3
In the present embodiment, for bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, it is carried out and tested
The experiment of card property.Broken+sorting is carried out to waste printed circuit board first, the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element.Multi-metal complex mixture is placed in the graphite earthenware of vacuum furnace
In pot.Then, vacuum furnace is sealed, starts vacuum-pumping system, works as vacuum<After 10Pa, it is filled with into heating furnace nacelle
Nitrogen, to reduce the volatilization of low-melting-point metal element and avoid METAL HEATING PROCESS process from aoxidizing.Start vacuum furnace power supply, heating
To 1100 DEG C, after many metal mixtures in graphite crucible are completely melt, mechanical agitation 5min, and it is incubated 10min.Then,
Melt temperature is reduced to 900 DEG C, adds in example 2 through once trapping the lead of bismuth element, contains lead quality in many metal mixtures
Amount reaches 50%, and melt liquid-liquid separation is into liquid copper and liquid lead.Melt temperature is reduced to 830 DEG C, liquid copper and liquid lead two
The further separation of phase, bismuth element selectivity fast enriching is into lead liquid phase.Keep 830 DEG C of melt temperature, mechanical agitation graphite
Liquid copper and liquid lead blend melt about 15min in crucible.In 830 DEG C of melt temperature standing 30min, liquid lead and liquid copper it
Between because there is density contrast, the melt in crucible is layered under gravity, forms that upper strata is liquid copper and lower floor is liquid
The layering melt of lead, the melt of upper lower leaf is poured out respectively.Thus, bismuth element divides from many metal mixtures of waste printed circuit board
Separate out and.Upper strata liquid copper continues on for other with the separation of targetedly metallic element and cycling and reutilization.Chemical analysis knot
Fruit shows that after 2 times trap bismuth element, the bismuth element mass content in lower floor's lead liquid has reached 0.152%, and in liquid copper
Bismuth element mass content be 0.004%, the most separation and concentrations of the bismuth element in many metal mixtures of waste printed circuit board are arrived
In lead liquid phase.
Embodiment 4
In the present embodiment, for bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, it is carried out and tested
The experiment of card property.Broken+sorting is carried out to waste printed circuit board first, the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element.Add and disassembled from electron wastes in multi-metal complex mixture
The release agent aluminium element got off, it is 8% to make aluminium element proportioning mass fraction shared in many metal mixtures, by what is configured
Multi-metal complex mixture is placed in the black-fead crucible of vacuum furnace.Then, vacuum furnace is sealed, starts vacuum suction system
System, works as vacuum<After 10Pa, nitrogen is filled with into heating furnace nacelle, to reduce the volatilization of low-melting-point metal element and avoid gold
Belong to heating process oxidation.Start vacuum furnace power supply, be heated to 1150 DEG C, treat that many metal mixtures in graphite crucible are complete
After fusing, mechanical agitation 5min, and it is incubated 5min.Then, reduction melt temperature adds trapping agent lead element, made to 1050 DEG C
Lead element proportioning mass fraction shared in graphite crucible melt is 50%, and melt liquid-liquid separation is into liquid copper and liquid lead.
Melt temperature is kept at 1050 DEG C, micro pregnant solution sodium oxide molybdena, regulation and control liquid copper and point of liquid lead two-phase are added in the melt
From rate, bismuth element selectivity fast enriching is into lead liquid phase.Melt temperature is reduced to 1000 DEG C, liquid in mechanical agitation graphite crucible
State copper and liquid lead blend melt about 10min.In 1000 DEG C of standing 10min of melt temperature, because depositing between liquid lead and liquid copper
In density contrast, the melt in crucible is layered under gravity, forms point that upper strata is liquid copper and lower floor is liquid lead
Layer melt, the melt of upper lower leaf is poured out respectively.Thus, bismuth element is isolated from many metal mixtures of waste printed circuit board
Come.Upper strata liquid copper continues on for other with the separation of targetedly metallic element and cycling and reutilization.Chemical analysis results table
Bright, after once trapping bismuth element, the bismuth element mass content in lower floor's lead liquid has reached 0.053%, and in liquid copper
Bismuth element mass content is 0.0025%, the most separation and concentrations of the bismuth element in many metal mixtures of waste printed circuit board to lead
In liquid phase.
Embodiment 5
In the present embodiment, for bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, it is carried out and tested
The experiment of card property.Broken+sorting is carried out to waste printed circuit board first, the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element.Add and disassembled from electron wastes in multi-metal complex mixture
The release agent aluminium element got off, it is 8% to make aluminium element proportioning mass fraction shared in many metal mixtures, by what is configured
Multi-metal complex mixture is placed in the black-fead crucible of vacuum furnace.Then, vacuum furnace is sealed, starts vacuum suction system
System, works as vacuum<After 10Pa, nitrogen is filled with into heating furnace nacelle, to reduce the volatilization of low-melting-point metal element and avoid gold
Belong to heating process oxidation.Start vacuum furnace power supply, be heated to 1150 DEG C, treat that many metal mixtures in graphite crucible are complete
After fusing, mechanical agitation 5min, and it is incubated 10min.Then, reduction melt temperature adds trapping agent lead element, made to 1050 DEG C
Lead element proportioning mass fraction shared in graphite crucible melt is 50%, and melt liquid-liquid separation is into liquid copper and liquid lead.
Melt temperature is kept at 1050 DEG C, micro pregnant solution sodium oxide molybdena, regulation and control liquid copper and point of liquid lead two-phase are added in the melt
From rate, bismuth element selectivity fast enriching is into lead liquid phase.Melt temperature is reduced to 1000 DEG C, liquid in mechanical agitation graphite crucible
State copper and liquid lead blend melt about 15min.In 1000 DEG C of standing 30min of melt temperature, because depositing between liquid lead and liquid copper
In density contrast, the melt in crucible is layered under gravity, forms point that upper strata is liquid copper and lower floor is liquid lead
Layer melt, the melt of upper lower leaf is poured out respectively.Thus, bismuth element is isolated from many metal mixtures of waste printed circuit board
Come.Upper strata liquid copper continues on for other with the separation of targetedly metallic element and cycling and reutilization.Chemical analysis results table
Bright, after once trapping bismuth element, the bismuth element mass content in lower floor's lead liquid has reached 0.067%, and in liquid copper
Bismuth element mass content is 0.0060%, the most separation and concentrations of the bismuth element in many metal mixtures of waste printed circuit board to lead
In liquid phase.
Embodiment 6
In the present embodiment, for bismuth element in many metal mixtures of waste printed circuit board enrichment with separating, it is carried out and tested
The experiment of card property.Broken+sorting is carried out to waste printed circuit board first, the metal in waste printed circuit board is isolated from nonmetallic
Come, obtain the multi-metal complex mixture containing bismuth element.Multi-metal complex mixture is placed in the graphite earthenware of vacuum furnace
In pot.Then, vacuum furnace is sealed, starts vacuum-pumping system, works as vacuum<After 10Pa, it is filled with into heating furnace nacelle
Nitrogen, to reduce the volatilization of low-melting-point metal element and avoid METAL HEATING PROCESS process from aoxidizing.Start vacuum furnace power supply, heating
To 1150 DEG C, after many metal mixtures in graphite crucible are completely melt, mechanical agitation 5min, and it is incubated 10min.Then,
Melt temperature is reduced to 1050 DEG C, adds in example 5 through once trapping the lead of bismuth element, makes lead element proportioning molten in graphite crucible
Shared mass fraction is 50% in body, and melt liquid-liquid separation is into liquid copper and liquid lead.Melt temperature is kept at 1050 DEG C,
Liquid copper is further separated with liquid lead two-phase, and bismuth element selectivity fast enriching is into lead liquid phase.Reduction melt temperature is arrived
1000 DEG C, liquid copper and liquid lead blend melt about 15min in mechanical agitation graphite crucible.In 1000 DEG C of standings of melt temperature
30min, because there is density contrast between liquid lead and liquid copper, the melt in crucible is layered under gravity, in formation
The layering melt that layer is liquid copper and lower floor is liquid lead, the melt of upper lower leaf is poured out respectively.Thus, bismuth element is from discarded
Separated in many metal mixtures of circuit board.Upper strata liquid copper continue on for it is other have targetedly metallic element separation with
Cycling and reutilization.Chemical analysis results show that after 2 times trap bismuth element, the bismuth element mass content in lower floor's lead liquid reaches
To 0.095%, and the bismuth element mass content in liquid copper is 0.0077%, the bismuth in many metal mixtures of waste printed circuit board
Element overwhelming majority separation and concentration is into lead liquid phase.
Claims (4)
1. the enrichment of bismuth element and separation method in a kind of many metal mixed resources of waste printed circuit board, it is characterised in that utilize gold
Belong to the selectivity distribution behavior and its control of the metallurgy feature and metallic element of liquid-liquid separation in liquid-phase separating system, lead to
Cross and add different release agents, trapping agent and pregnant solution element and use different technological parameters, regulation and control metallic element is in liquid
Apportionment ratio in phase-separation system, makes the Biosorption of Metal Elements that is recovered and is fixed in trapping agent liquid phase, returned so as to realize
Receive metallic element to separate from many metal mixtures of waste printed circuit board, be finally able to green reclaim and cycling and reutilization, wrap
Include following steps：
Step 1 carries out broken+sorting to waste printed circuit board, and the metal in waste printed circuit board is separated from nonmetallic, obtained
Multi-metal complex mixture that must be containing bismuth element；
Step 2 adds release agent silicon or aluminium element in multi-metal complex mixture, matches silicon or aluminium element mixed in many metals
Shared mass fraction is 5%~18% in compound, and the multi-metal complex mixture configured is placed in the graphite of vacuum furnace
In crucible；
After the sealing of step 3 vacuum furnace, start vacuum-pumping system, after vacuum is less than 10Pa, is filled with nitrogen, reduces low
The volatilization of melting point metals element and metal is avoided to aoxidize；
Step 4 starts vacuum furnace power supply, is heated to 1100~1150 DEG C, treats that many metal mixtures in graphite crucible are complete
After fusing, mechanical agitation 5 minutes, and it is incubated 5~10min；
Step 5 reduces melt temperature, and adds trapping agent lead element, the matter for making lead element proportioning shared in graphite crucible melt
It is 30%~60% to measure fraction, and melt liquid-liquid separation is into liquid copper and liquid lead；
Step 6 adds pregnant solution, regulation and control liquid copper and the separation rate of liquid lead two-phase, arrives the selective fast enriching of bismuth element
In lead liquid phase, the pregnant solution of addition is the oxide of alkali metal；
Step 7 reduces melt temperature near liquid copper phase fusing point, and liquid copper is mixed with liquid lead in mechanical agitation graphite crucible
10~15min of melt；
Step 8 keeps melt temperature to stand 10~30min, because there is density contrast between liquid lead and liquid copper, in Action of Gravity Field
Melt in lower crucible is layered, and forms the layering melt that upper strata is liquid copper and lower floor is liquid lead, by upper strata liquid copper
Pour out, continue on for other with the separation of targetedly metallic element and cycling and reutilization；
Then step 9 is poured out the remaining lower floor's liquid lead for having trapped bismuth element in crucible, and detect bismuth element in liquid lead
Mass content, if bismuth element mass content be less than 5%, liquid lead return in step 5 recycle, as trapping agent lead member
Element is used for the enrichment of bismuth element in many metal mixed resources of waste printed circuit board of next batch with separating.
2. enrichment and separation method according to bismuth element in many metal mixed resources of waste printed circuit board described in claim 1, its
It is characterised by：In step 2, the release agent aluminium element of addition is mainly derived from the aluminum metal that electron wastes are dismantled, and makes
The metal of electron wastes obtains comprehensive cyclic utilization.
3. enrichment and separation method according to bismuth element in many metal mixed resources of waste printed circuit board described in claim 1, its
It is characterised by：In step 9, that pours out has trapped lower floor's liquid lead of bismuth element, is cooled to 350~450 DEG C, is separated out in melt few
In Crystal Solid Copper is measured, then using centrifugation or solid-liquid filtration isolation technics, liquid lead is further separated with copper；Thus, bismuth
Element is separated from waste printed circuit board multi-metal complex mixture, and is recycled.
4. enrichment and separation method according to bismuth element in many metal mixed resources of waste printed circuit board described in claim 3, its
It is characterised by：If the bismuth element mass content in liquid lead has now reached predetermined value, coloured smelting factory is sent to, is made after refining
Make metallurgical addition agent or solder.
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| CN109609778B (en) * | 2019-02-19 | 2020-10-09 | 东北大学 | Method for removing gallium from primary aluminum by utilizing metal extraction |
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|---|---|---|---|---|
| CN1760382A (en) * | 2005-11-03 | 2006-04-19 | 上海交通大学 | Vacuum distillation method for separating bismuth element from mixed metals in worn-out printing circuit board |
| CN101886174A (en) * | 2010-06-23 | 2010-11-17 | 郴州雄风稀贵金属材料股份有限公司 | Process for refining high-purity bismuth from bismuth-containing material generated from anode mud recovery |
| CN102218439A (en) * | 2011-01-24 | 2011-10-19 | 同济大学 | Method for pyrolysis separation of valuable components from substrates of waste printed circuit boards |
| CN104313332A (en) * | 2014-10-15 | 2015-01-28 | 中国科学院金属研究所 | Self-assembly separation and resource recycling method for multi-metal components in electronic waste |
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|---|---|---|---|---|
| CN1760382A (en) * | 2005-11-03 | 2006-04-19 | 上海交通大学 | Vacuum distillation method for separating bismuth element from mixed metals in worn-out printing circuit board |
| CN101886174A (en) * | 2010-06-23 | 2010-11-17 | 郴州雄风稀贵金属材料股份有限公司 | Process for refining high-purity bismuth from bismuth-containing material generated from anode mud recovery |
| CN102218439A (en) * | 2011-01-24 | 2011-10-19 | 同济大学 | Method for pyrolysis separation of valuable components from substrates of waste printed circuit boards |
| CN104313332A (en) * | 2014-10-15 | 2015-01-28 | 中国科学院金属研究所 | Self-assembly separation and resource recycling method for multi-metal components in electronic waste |
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