CN109234537A - A kind of recovery method as resource of tin-coated copper rice - Google Patents
A kind of recovery method as resource of tin-coated copper rice Download PDFInfo
- Publication number
- CN109234537A CN109234537A CN201811218114.8A CN201811218114A CN109234537A CN 109234537 A CN109234537 A CN 109234537A CN 201811218114 A CN201811218114 A CN 201811218114A CN 109234537 A CN109234537 A CN 109234537A
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- Prior art keywords
- tin
- coated copper
- copper rice
- silicone oil
- resource
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
-
- 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
- C22B25/02—Obtaining tin by dry processes
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention provides a kind of recovery method as resource of tin-coated copper rice, and tin-coated copper rice is placed in container first, and silicone oil is added, it is heated to the tin fusing on tin-coated copper rice surface layer, useless tin-coated copper rice 2-3h is stirred, the tin fusing on tin-coated copper rice surface layer is uniformly dissociated into tiny liquid in silicone oil；While not stopping stirring operation, stop heating, until container is cooled to room temperature, tiny liquid tin is converted into solid-state tin particles and is suspended in silicone oil；Stop stirring, collects treated silicone oil out of container immediately；Silicone oil is centrifugated, pure silicone oil and nanometer tin powder are respectively obtained；Nanometer tin is sent into tube furnace, nanometer tin is contacted with air in tube furnace, is heated to 300-320 DEG C, is kept the temperature cooling after 30min, is obtained nano tin dioxide powder.Present invention process is simple and efficient, easy to operate, and separation and recovery effect is good, can further industrialization amplification production.
Description
Technical field:
The invention belongs to secondary resource recycling fields, and in particular to a kind of recovery method as resource of tin-coated copper rice.
Technical background:
Existing waste tin-plated electric wires largely use copper rice machine to be handled, and copper rice machine is for crushing to waste and old copper wire
The machinery that copper and plastics are separated.Waste tin-plated electric wires obtain useless tin-coated copper rice after the processing of copper rice machine.Tin-coated copper rice is useless
The new raw material of industry of one kind of cable production, its separation and recovery not only can be improved the utilization rate of metal, improve regenerated resources
Added value, and can be to avoid the pollution to bad border.
From the prior art, from the point of view of the recovery method of tin-coated copper rice, mainly there are an acid-hatching of young eggs and two kinds of electrolysis method, such as in
State's patent of invention 200910090636.9 proposes that copper sulphate-dump leaching process recycles copper and tin in waste and old tinned wird, middle promulgated by the State Council
Bright patent 201010279564.5 recycles tin from copper rice using techniques, these methods such as being electrolysed after the processing of dedicated leaching equipment again
There is the problems such as cost recovery is high, process flow is long.
There is secondary pollution in all methods handled with chemical reagent, and achievement is high, long flow path, mass recycling effect
Fruit is undesirable.Therefore, it is necessary to research and develop a kind of more efficient, low cost and economic friendly method, the tin-coated copper rice that gives up is solved
Separation and recovery problem.
Applicant is had studied the recovery method as resource of tin-coated copper rice, tin is made by the way of heating on the basis of early period
Fusing, the tin of molten state enter under stirring in liquid heat conductive oil, have had been surprisingly found that the high-valued resource reclaim of tin-coated copper rice
Method.
Summary of the invention:
Technical problem to be solved by the invention is to provide a kind of recovery method as resource of tin-coated copper rice, copper and tin are realized
High-valued recycling.
A kind of recovery method as resource of tin-coated copper rice of the present invention, is realized by following steps:
1), tin-coated copper rice is placed in container, silicone oil is added, tin-coated copper rice is completely submerged in silicone oil, is heated to tin plating
The tin on copper rice surface layer melts, and stirs useless tin-coated copper rice 2-3h by agitating device, the tin fusing on tin-coated copper rice surface layer is cut in stirring
Under shear force effect, tiny liquid is uniformly dissociated into silicone oil；
2), while not stopping stirring operation, stop heating, until container is cooled to room temperature, tiny liquid tin turns
Solid-state tin particles are turned to be suspended in silicone oil；Stop stirring, collects treated silicone oil out of container immediately, and in collection vessel
Copper rice after portion's detin；
3), silicone oil is sent into centrifuge and is centrifuged, pure silicone oil and nanometer tin powder are respectively obtained；It will receive
Rice tin is sent into tube furnace, and nanometer tin is contacted with air in tube furnace, is heated to 300-320 DEG C, is kept the temperature cooling after 30min, is obtained
To nano tin dioxide powder.
The line footpath of the tin-coated copper rice is 2-4mm, length 5-12mm.
The ratio that container is added in the tin-coated copper rice and silicone oil is 1g:10ml.
It is 240-250 DEG C by external heating device computer heating control vessel temp in the step 1).
The step 1) and 2) in, agitating device stir when revolving speed be 500-1000rpm.
In the step 3), the revolving speed that silicone oil is centrifuged is 5000-10000rpm.
Technical principle of the invention are as follows:
Tin-coated copper rice is carried out to oil bath stirring under tin fusing point (231.89 DEG C) temperatures above first, tin-coated copper rice surface layer
Tin fusing, liquid tin is constantly sheared under stirring, and cutting is more tiny liquid individual；Since tin-coated copper rice submerges
In a large amount of silicone oil, mass per volume score of the tin in silicone oil is very low, and liquid tin is easily dispersed inside silicone oil, special
It is not lasting stirring shear action, so that liquid tin is uniformly distributed in the silicone oil constantly moved；Tin is reduced in temperature
During fusing point is below, stirring action is continued for, and liquid tin has no chance to condense together, be cooled to tin fusing point hereinafter,
Liquid tin is changed into solid-state tin particles, since the partial size of particle is very small (nanoscale), is suspended in silicone oil；It is cooled to room
Temperature stops stirring, after silicone oil is separated with the copper rice of detin, silicone oil is centrifuged, and realizes point of silicone oil and nanometer tin
From；Nanometer tin is placed in tube furnace and is carried out, is contacted with air, the nanometer tin high temperature at a temperature of 300-320 DEG C in tube furnace
Oxidation, the silicone oil on surface layer are thermally decomposed, and nanometer tin is reacted with oxygen generates nano-stannic oxide.
Using the tin of heating tin-coated copper rice stirring removing molten state, and the tin of molten state is dispersed in liquid medium oil,
By way of configuring suitable silicone oil additional proportion and stirring, it is evenly distributed in silicone oil；It is cooled to tin fusing point temperature below
When spending, then a nanometer tin particles are converted into.
The present invention has had been surprisingly found that tin can be uniformly dispersed in silicone oil during recycling tin-coated copper rice, with existing skill
Unlike art, the separation that previous recovery technology focuses on removing tin, realizes tin and copper rice, such as: made using heating tin-coated copper rice
Tin fusing is obtained, then is separated tin by modes such as centrifuge separations, realizes the recycling of copper rice and simple substance tin；What the present invention used
Method is several tiny parts constantly to be cut into, especially in a large amount of sticky silicon using tin is melted under stirring
In oil, the liquid tin being constantly sheared can disperse well, once temperature is down to fusing point hereinafter, can be obtained nanoscale tin
Grain.
In the present invention, according to Medium Oil ratio it is less, the molten state tin of tin-coated copper rice collides general in Medium Oil
Rate is very big, can polymerize under mutual tension force effect, be cooled to tin fusing point or less and then form larger sized simple substance tin；According to
Medium Oil be the low diesel oil etc. of viscosity, the tin of molten state is difficult to be dispersed in Medium Oil, sinks to medium under the effect of gravity
Oily bottom, also can be very big in the probability that the region of bottom is mutually collided, and forms large scale tin when being cooled to tin fusing point following temperature；
In addition, Medium Oil is hardly formed dispersion if not continuing stirring action, the tin of molten state can persistently by shear action,
Until clipping to dimension limit, the granular system of dispersion is formed in Medium Oil.
The nanometer tin that the present invention obtains is centrifugally separating to obtain in silicone oil, is wrapped up outside the tin particles recycled
One layer of silicone oil, in the thermal oxidation process then carried out, silicone oil is thermally decomposed first, avoids prior art preparation nanometer titanium dioxide
Existing agglomeration during tin.Prior art preparation nano-stannic oxide, generally using tin source with SnCl4.5H2O or
SnCl2.2H2O is reacted by a series of wet chemistry, and finally drying obtains, it is easy to there is agglomeration, this is because
Surface tension during drying due to water is very big, under hydroxyl bridging effect makes that hard aggregation occurs between nano particle.
And method of the invention does not have any moisture to participate in, and is to be oxidized to what stannic oxide obtained by tin.
The beneficial effects of the present invention are:
1, tin-coated copper rice is subjected to high-valued resource reclaim, obtains pure nano-stannic oxide and detin copper rice；
2, whole process does not use chemical agent, and using the characteristic that tin molten state and silicone oil are sticky, shearing is separated into
Nanoparticle system will not generate any secondary pollution；
3, present invention process is simple and efficient, easy to operate, and separation and recovery effect is good, can further industrialization amplification production.
Detailed description of the invention:
Fig. 1 is a kind of process flow chart of the recovery method as resource of tin-coated copper rice.
Specific embodiment:
Embodiment 1
It is 2-4mm by 200g line footpath, the tin-coated copper rice that length is 5-12mm is placed in container, and 2L silicone oil, tin-coated copper is added
Rice is completely submerged in silicone oil, is heated to the tin fusing on 240 DEG C of tin-coated copper rice surface layers, stirs useless tin-coated copper rice by agitating device
3h, speed of agitator 800rpm, the tin fusing on tin-coated copper rice surface layer, in the case where stirring shearing force, are uniformly dissociated in silicone oil
At tiny liquid；While not stopping stirring operation, stop heating, until container is cooled to room temperature, tiny liquid
State tin is converted into solid-state tin particles and is suspended in silicone oil；Stop stirring, collects treated silicone oil out of container immediately, and collect
Copper rice inside container after detin；Silicone oil is sent into centrifuge and is centrifuged, centrifuge speed 10000rpm, respectively
Obtain pure silicone oil and nanometer tin powder；Nanometer tin is sent into tube furnace, nanometer tin is contacted with air in tube furnace, heating
To 300 DEG C, cooling after 30min is kept the temperature, nano tin dioxide powder is obtained.
Experimental result:
1, completely, copper rice is changed into brassy by original silvery white to the removing of detin copper rice surface layer tin coating；
2, nano-stannic oxide white powder 2.623g, average grain diameter 60nm are obtained.
Claims (6)
1. a kind of recovery method as resource of tin-coated copper rice, it is characterised in that: realized by following steps:
1), tin-coated copper rice is placed in container, silicone oil is added, tin-coated copper rice is completely submerged in silicone oil, is heated to tin-coated copper rice
The tin on surface layer melts, and stirs useless tin-coated copper rice 2-3h, the tin fusing on tin-coated copper rice surface layer, in stirring shearing force by agitating device
Under effect, tiny liquid is uniformly dissociated into silicone oil；
2), while not stopping stirring operation, stop heating, until container is cooled to room temperature, tiny liquid tin is converted into
Solid-state tin particles are suspended in silicone oil；Stop stirring, collect treated silicone oil out of container immediately, and is de- inside collection vessel
Copper rice after tin；
3), silicone oil is sent into centrifuge and is centrifuged, pure silicone oil and nanometer tin powder are respectively obtained；By nanometer tin
It is sent into tube furnace, nanometer tin is contacted with air in tube furnace, is heated to 300-320 DEG C, is kept the temperature cooling after 30min, is received
Rice stannic oxide powder.
2. a kind of recovery method as resource of tin-coated copper rice according to claim 1, it is characterised in that: the tin-coated copper rice
Line footpath be 2-4mm, length 5-12mm.
3. a kind of recovery method as resource of tin-coated copper rice according to claim 1, it is characterised in that: the tin-coated copper rice and
The ratio that container is added in silicone oil is 1g:10ml.
4. a kind of recovery method as resource of tin-coated copper rice according to claim 1, it is characterised in that: in the step 1),
It is 240-250 DEG C by external heating device computer heating control vessel temp.
5. a kind of recovery method as resource of tin-coated copper rice according to claim 1, it is characterised in that: the step 1) and 2)
In, revolving speed when agitating device stirs is 500-1000rpm.
6. a kind of recovery method as resource of tin-coated copper rice according to claim 1, it is characterised in that: in the step 3),
The revolving speed that silicone oil is centrifuged is 5000-10000rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811218114.8A CN109234537A (en) | 2018-10-19 | 2018-10-19 | A kind of recovery method as resource of tin-coated copper rice |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811218114.8A CN109234537A (en) | 2018-10-19 | 2018-10-19 | A kind of recovery method as resource of tin-coated copper rice |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109234537A true CN109234537A (en) | 2019-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811218114.8A Withdrawn CN109234537A (en) | 2018-10-19 | 2018-10-19 | A kind of recovery method as resource of tin-coated copper rice |
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| CN (1) | CN109234537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113060758A (en) * | 2021-05-07 | 2021-07-02 | 云南锡业研究院有限公司 | Method for preparing stannic oxide and stannate by using tin-copper slag |
-
2018
- 2018-10-19 CN CN201811218114.8A patent/CN109234537A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113060758A (en) * | 2021-05-07 | 2021-07-02 | 云南锡业研究院有限公司 | Method for preparing stannic oxide and stannate by using tin-copper slag |
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| Date | Code | Title | Description |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190118 |
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| WW01 | Invention patent application withdrawn after publication |