CN106893876A - A kind of recovery method of useless tinned wire - Google Patents
A kind of recovery method of useless tinned wire Download PDFInfo
- Publication number
- CN106893876A CN106893876A CN201710003497.6A CN201710003497A CN106893876A CN 106893876 A CN106893876 A CN 106893876A CN 201710003497 A CN201710003497 A CN 201710003497A CN 106893876 A CN106893876 A CN 106893876A
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- CN
- China
- Prior art keywords
- tin
- pyrolysis
- copper cash
- useless
- useless tinned
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Centrifugal Separators (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of recovery method of useless tinned wire, useless tinned wird is placed in first carry out traditional vacuum pyrolysis in the centrifugal separating device of vacuum tank, the plastics pyrolysis on useless tinned wird surface, cooling liquid is liquid oil after pyrolysis devolatilization thing is separated from vacuum tank；While pyrolysis, the carbide on useless tinned wird surface, most of tin coating are separated with copper cash using centrifugal separating device, the very thin tin of another part is remained on copper cash；Then copper cash is electrolysed, the tin in copper line surface is oxidized to tin ion and enters in electrolyte, and the tin in electrolyte is reduced into metal sponge tin on negative electrode；Copper cash cleaning, watery hydrochloric acid are soaked again, is cleaned again, that is, obtain the copper cash of light.Present invention process method is simple, and organic efficiency is high, low cost, and the resource that copper, tin, the plastics in useless tinned wire all obtain better quality is reclaimed.
Description
Technical field：
The invention belongs to secondary resource recycling field, and in particular to a kind of recovery method of useless tinned wire.
Technical background：
As developing rapidly for power communication cause, society increasingly increase to the demand of electric wire, the thing followed is given up
Electric wire is also growing day by day, adds that metals resources are increasingly deficient, and World Copper, tin price can be in any more, and waste electric wire cable is returned
Receive all significant to economy and society.Because traditional conductor copper cash has partial oxidation in high temperature extrusion, and easily
Easily there is loose contact when wire is connected, therefore, existing copper conductor is universal good to make it have in electroplating surfaces with tin
Corrosion resistance and welding performance.
It is low due to being difficult wire stripping or wire stripping efficiency for most of useless tinned wirds, generally using crushing technology treatment.Powder
Broken technology is that waste electric wire cable is directly broken into graininess by plant equipment such as cutting machine and pulverizers, then is set by sorting
It is standby to separate plastics and metal.As can be seen that the recovery technology of existing waste electric wire cable focuses on separation copper and plastics,
And it is helpless to the separation and recovery of the tin coating on copper conductor.For the separation and recovery skill of the tin coating on tinned wird surface of giving up
For art, from the prior art, mainly there are two kinds of the acid-hatching of young eggs and electrolysis, but there is cost recovery is high, technological process is long etc.
Problem.
Accordingly, it would be desirable to research and develop a kind of method that tin, copper, plastics are completely separated from useless tinned wire, efficient resource is realized
Change.
The content of the invention：
The technical problems to be solved by the invention are to provide high useless of a kind of simple, pollution-free method, low cost, the rate of recovery
The recovery method of tinned wire.
A kind of recovery method of useless tinned wire of the present invention, is realized by following steps：
1) traditional vacuum pyrolysis：Useless tinned wird is placed in the centrifugal separating device of vacuum tank, 450 DEG C of guarantors are warming up to
Constant temperature 30min is held, the plastics pyrolysis on tinned wird surface of giving up, cooling liquid is liquid after pyrolysis devolatilization thing is separated from vacuum tank
Body oil；While pyrolysis, the carbide on useless tinned wird surface, most of tin coating and copper cash are divided using centrifugal separating device
From the very thin tin of another part is remained on copper cash；
2) it is electrolysed：By step 1) copper cash that obtains is fitted into the anode frame that carbon steel is made, using carbon steel sheet as negative electrode, is electrolysed
Liquid is NaSnO3- NaOH solution, naoh concentration is 50g/L, control electric current density 180A/m2, tank voltage is 0.4V, copper cash
Tin on surface is oxidized to tin ion and enters in electrolyte, and the tin in electrolyte is reduced into metal sponge tin on negative electrode, when
Stop electrolysis when thering is bubble to produce in anode frame；
3) polish：By step 2) copper cash that obtains inserts in clear water and cleans, and to place into and soak 10min in dilute hydrochloric acid solution,
Cleaned with clear water again, that is, obtain the copper cash of light.
A kind of recovery method of useless tinned wire of the present invention, the system pressure of traditional vacuum pyrolysis is 20kpa.
A kind of recovery method of useless tinned wire of the present invention, the centrifugal rotational speed of traditional vacuum pyrolytic process keeps 800rpm.
A kind of recovery method of useless tinned wire of the present invention, tin ion concentration is 18g/L in electrolytic process.
A kind of recovery method of useless tinned wire of the present invention, dilute hydrochloric acid solution concentration is 1mol/L in polishing process.
Using the recovery method of a kind of useless tinned wire of above-mentioned technical proposal, its operation principle and process are summarized as follows：
Useless tinned wire is loaded the present invention centrifugal separating device of vacuum tank --- and pyrolysis turns with centrifugal compound machine
In drum, rotary drum is that hollow and side and bottom carry sieve aperture, and system is carried out into vacuumize process, is heated to useless tinned wird epidermis
The pyrolysis temperature of plastics, plastics are pyrolysis devolatilization, and volatile matter is extracted out and is cooled to oil, and carbon distribution has been remained in copper cash after plastic skin pyrolysis
Surface；Start centrifugal separating device --- rotary drum simultaneously, the carbon remained in copper line surface is with most of molten state tin in centrifugal force
In the presence of throw away, separated with copper cash, only remained a small amount of tin on the surface of copper cash；Then separated by the way of electrolysis
Recovery remains in the tin of copper line surface.
The inventors discovered that, if individually using vacuum pyrolysis centrifugal separation method, the tin for remaining in copper line surface cannot
More thoroughly reclaim；According to the mode of direct wire stripping+electrolysis, required amount of reagent is huge, high energy consumption, high cost；This hair
The bright method using separating+being electrolysed vacuum pyrolysis, eliminates wire stripping process, and the pyrolysis oil obtained after plastic skin pyrolysis can be used as
Fuel, most of tin is recycled by physical process, and under vacuum conditions, will not under the protection of plastic skin pyrolysis carbon distribution
Oxidation, obtains the simple substance tin of higher quality；Then the recovery of a small amount of tin is realized by electrolytic process.It has been found that useless at present
Tin accounts for the 3% even more many of total metal content in tinned wire, in the present invention, 90% is removed by way of traditional vacuum is separated
Tin above (this process substantially carries out zero cost and reclaims tin), remaining less than 10% tin transfers to electrolytic process to complete.It is logical
Techno-economic comparison is crossed to understand：The present invention combines vacuum pyrolysis centrifugal separation method and electrolytic method, eliminates wire stripping
Process, greatly reduces electrolysis energy consumption, electrolysis reagent for pure electrolytic method, significantly reduces cost recovery, improves
Organic efficiency, has obtained unexpected technique effect.
Technique effect after two kinds of technologies are combined is comprehensive more superior than each technical characteristic effect.
The beneficial effects of the invention are as follows：
A kind of recovery method of useless tinned wire of the present invention, process is simple, and organic efficiency is high, low cost, gives up tin plating
The resource that copper, tin, plastics in electric wire all obtain better quality is reclaimed, and is suitable for large-scale industrialization recycle.
Brief description of the drawings：
Fig. 1 is a kind of process chart of the recovery method of useless tinned wire.
Specific embodiment：
Embodiment 1
1) the useless tinned wirds of 1kg are taken to be placed in the centrifugal separating device of vacuum tank, 450 DEG C of holding constant temperature are warming up to
30min, the pressure in system is not higher than 20kpa, the plastics pyrolysis on tinned wird surface of giving up, and pyrolysis devolatilization thing is from vacuum tank
Cooling liquid is liquid oil after separation；While pyrolysis, using centrifugal separating device by the carbide on useless tinned wird surface, big
Part tin coating is separated with copper cash, and rotating speed keeps 800rpm, the very thin tin of another part to remain on copper cash；
2) it is electrolysed：By step 1) copper cash that obtains is fitted into the anode frame that carbon steel is made, using carbon steel sheet as negative electrode, is electrolysed
Liquid is NaSnO3- NaOH solution, wherein tin ion concentration are 18g/L, and naoh concentration is 50g/L, control electric current density
180A/m2, tank voltage is 0.4V, and the tin in copper line surface is oxidized to tin ion and enters in electrolyte, by electrolyte on negative electrode
In tin be reduced into metal sponge tin, when there is bubble to produce in anode frame stop electrolysis；
3) by step 2) copper cash that obtains inserts in clear water and cleans, and place into and soak in the dilute hydrochloric acid solution of 1mol/L
10min, then cleaned with clear water, that is, obtain the copper cash of high-purity.
Experimental result is as follows：
Useless tinned wird recovery product situation：
Pyrolysis oil：153g
Carbon distribution：62g
The tin that vacuum pyrolysis is centrifugally separating to obtain：27.3g
Copper cash：743g (copper contents：99.91%)
The spongy tin that electrolytic process is obtained：2.6g.
Claims (5)
1. a kind of recovery method of useless tinned wire, it is characterised in that：Comprise the following steps：
1) traditional vacuum pyrolysis：Useless tinned wird is placed in the centrifugal separating device of vacuum tank, 450 DEG C is warming up to and is kept permanent
Warm 30min, the pressure in system is 20kpa, and the plastics pyrolysis on tinned wird surface of giving up, pyrolysis devolatilization thing divides from vacuum tank
It is liquid oil from rear cooling liquid；While pyrolysis, using centrifugal separating device by the carbide on useless tinned wird surface, big portion
Tin coating is divided to be separated with copper cash, the very thin tin of another part is remained on copper cash；
2) it is electrolysed：By step 1) obtain copper cash be fitted into the anode frame that carbon steel is made, using carbon steel sheet as negative electrode, electrolyte is
NaSnO3- NaOH solution, naoh concentration is 50g/L, control electric current density 180A/m2, tank voltage is 0.4V, copper line surface
On tin be oxidized to tin ion into electrolyte, the tin in electrolyte is reduced into metal sponge tin on negative electrode, work as anode
Stop electrolysis when inframe has bubble to produce；
3) polish：By step 2) copper cash that obtains inserts in clear water and cleans, and to place into and soak 10min in dilute hydrochloric acid solution, then use
Clear water is cleaned, that is, obtain the copper cash of light.
2. the recovery method of a kind of useless tinned wire according to claim 1, it is characterised in that：The body of traditional vacuum pyrolysis
It is that pressure is 20kpa.
3. the recovery method of a kind of useless tinned wire according to claim 1 and 2, it is characterised in that：Traditional vacuum is pyrolyzed
The centrifugal rotational speed of process keeps 800rpm.
4. the recovery method of a kind of useless tinned wire according to claims 1 to 3 any one, it is characterised in that：Electrolysis
During tin ion concentration be 18g/L.
5. the recovery method of a kind of useless tinned wire according to Claims 1-4 any one, it is characterised in that：Polishing
During dilute hydrochloric acid solution concentration be 1mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710003497.6A CN106893876B (en) | 2017-01-04 | 2017-01-04 | A kind of recovery method of useless tinned wire |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710003497.6A CN106893876B (en) | 2017-01-04 | 2017-01-04 | A kind of recovery method of useless tinned wire |
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| CN106893876A true CN106893876A (en) | 2017-06-27 |
| CN106893876B CN106893876B (en) | 2019-01-15 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61159580A (en) * | 1985-01-08 | 1986-07-19 | Tamagawa Kikai Kinzoku Kk | Method for dissolving and removing tin or tin-lead alloy layer on surface of copper or copper alloy material |
| CN101625915A (en) * | 2009-08-06 | 2010-01-13 | 中南大学 | Method for recycling waste tin-plated electric wires |
| CN105861837A (en) * | 2015-01-23 | 2016-08-17 | 重庆宇立金属制品有限公司 | Comprehensive recycling method of nickel-iron matrix tinned copperized electronic waste |
-
2017
- 2017-01-04 CN CN201710003497.6A patent/CN106893876B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61159580A (en) * | 1985-01-08 | 1986-07-19 | Tamagawa Kikai Kinzoku Kk | Method for dissolving and removing tin or tin-lead alloy layer on surface of copper or copper alloy material |
| CN101625915A (en) * | 2009-08-06 | 2010-01-13 | 中南大学 | Method for recycling waste tin-plated electric wires |
| CN105861837A (en) * | 2015-01-23 | 2016-08-17 | 重庆宇立金属制品有限公司 | Comprehensive recycling method of nickel-iron matrix tinned copperized electronic waste |
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| CN106893876B (en) | 2019-01-15 |
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Effective date of registration: 20181123 Address after: Room 840, No. 76 Xiyuan Lane, Shandong Road, Nanhu District, Jiaxing City, Zhejiang Province Applicant after: Jiaxing Katie Marketing Planning Co., Ltd. Address before: 410100 new Changhai center service outsourcing base, No. 29, A, Changsha economic and Technological Development Zone, Changsha, Hunan, 3, 2 floor 204 Applicant before: Changsha convergent Environment Technology Co., Ltd. |
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Effective date of registration: 20201015 Address after: 241000 third floor, citizen service center, Jishan Town Economic Development Zone, Nanling County, Wuhu City, Anhui Province Patentee after: Nanling County Construction Investment Co., Ltd Address before: Room 840, No. 76 Xiyuan Lane, Shandong Road, Nanhu District, Jiaxing City, Zhejiang Province Patentee before: JIAXING KAIDI MARKETING PLANNING Co.,Ltd. |