CN108913899A - A kind of device recycling metal and energy gas from waste and old solar panels - Google Patents
A kind of device recycling metal and energy gas from waste and old solar panels Download PDFInfo
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- CN108913899A CN108913899A CN201810598131.2A CN201810598131A CN108913899A CN 108913899 A CN108913899 A CN 108913899A CN 201810598131 A CN201810598131 A CN 201810598131A CN 108913899 A CN108913899 A CN 108913899A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000007789 sealing Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims description 15
- 229910006295 Si—Mo Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 24
- 230000008569 process Effects 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 229910052738 indium Inorganic materials 0.000 description 10
- 229910052733 gallium Inorganic materials 0.000 description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- 229910052732 germanium Inorganic materials 0.000 description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005272 metallurgy Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052571 earthenware Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- BYDQGSVXQDOSJJ-UHFFFAOYSA-N [Ge].[Au] Chemical compound [Ge].[Au] BYDQGSVXQDOSJJ-UHFFFAOYSA-N 0.000 description 1
- DECJQEOSXYARRQ-UHFFFAOYSA-L [OH-].[OH-].[Ge+2] Chemical compound [OH-].[OH-].[Ge+2] DECJQEOSXYARRQ-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- -1 copper therein Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/02—Combustion or pyrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of from waste and old solar panels recycles the device of metal and energy gas.Described device includes multi-temperature zone vacuum heater, alundum tube, assembled crucible, vacuum pump and gas bottle；The alundum tube is placed in multi-temperature zone heating device furnace, and assembled crucible is placed in alundum tube, and assembled crucible is formed by several crucible base assembly, and each crucible base corresponds to the position placement of the different heating warm area of multi-temperature zone vacuum heater；The entrance of alundum tube is equipped with sealing cover A, sealing cover A is equipped with vent valve and atmospheric pipe, the outlet of alundum tube is equipped with sealing cover B, sealing cover B is equipped with the gas-guide tube being controlled to a vacuum pump, gas-guide tube is equipped with vacuum pump valve, the gas outlet of vacuum pump is connect by conveyance conduit with gas bottle, and atmospheric pipe, vent valve and bottle valve are equipped in conveyance conduit.The arrangement achieves the efficient accurate recycling of metal, organic matter and silicon raw material in waste and old solar panels, have structure simple, high efficiente callback, environmental-friendly feature.
Description
Technical field
The present invention relates to solid waste resource recovery technical fields, and in particular to one kind recycles gold from waste and old solar panels
Belong to the device with energy gas.
Background technique
Solar energy be acknowledged as 21 century most clean, the energy abundant, in recent years, since energy crisis is gradually deepened,
The expanded production of solar panel and application.The service life of solar panels, domestic annual solar panels were raw generally in 15 to 20 years
Yield has reached 28.14% in 2016 all in Rapid Expansion, although the relevant solid waste of heliotechnics and traditional energy
The waste quantity of generation is compared to less, but in following 5 to 10 years, it will a large amount of waste and old solar energy electroplax occurs urgently
Processing.Therefore, it is badly in need of the relevant technologies and equipment handled solar energy electroplax, at present to cope with the waste problem that will be faced.
The structure of solar energy electroplax from top to bottom mainly include synthetic resin outer membrane, tempered glass, tin copper-clad conducting wire, stannic oxide, indium,
The rare metals such as gallium, germanium, crystalline silicon, zinc oxide and aluminum base use EVA (ethylene-ethyl acetate copolymer) between each component
The fixed bonding of equal organic bonds, the metals such as copper therein, indium, gallium, germanium are all to belong to more rare, and more expensive gold
Belong to, especially indium, gallium, the germanium mineral products that in nature are not elemental, be essentially all in the form of association existing for, right and wrong
The metal resource of Chang Zhengui.Therefore be necessary for the recycling of metal in waste and old solar panels, for resource can
Lasting exploitation has great importance.
It is also considerably less for the report of the recycling of metal in waste and old solar panels at present, and be using " concentrated acid dissolution+
The method of Chemical Leaching "：CN103184338A provides a kind of CIGS thin-film solar plate recovery method, first by the sun
Energy plate is broken, then utilizes H2SO4+H2O2System filtering is leached, and P is then passed through2O2+ kerosene, HCl, lye are extracted and are soaked
The hydroxide solution of In, Se, Cu are obtained out, and metal Ga is then obtained by the method for being electrolysed and precipitating.The method can be high
Effect recycling rare metal, process is also fairly simple, but can generate a large amount of soda acid in the process, contain metal ion and oxidisability
Stronger waste water, processing difficulty is big, is not a kind of recovery method of green.
CN103199148A provides a kind of method that gallium, indium, germanium are recycled from waste film solar battery, utilizes sulphur
Acid and nitric acid mixed oxidization solar panels fragment obtain the first separation containing gallium, indium, germanium, cadmium, copper, tin, zinc metal ion
Then at least one of zinc, aluminium, magnesium is added by adjusting pH precipitation and separation copper, cadmium in liquid, adjust pH and displace gallium, indium, germanium, tin
And metal mixed filter residue is obtained by filtration, gallium then is obtained by the way that lye dissolution gallium is added and is electrolysed, next by indium, germanium gold
Belong to and being dissolved in solid addition acid solution, passes through P2O2+ kerosene system, lye are stripped, are electrolysed and are precipitated, obtain indium metal and
Hydroxide germanium precipitating, obtains germanium metal by roasting reduction method.The method can equally be recovered to rare metal, but method
Process is complicated, and repeatedly uses the industrial chemicals such as strong acid, highly basic, generates a large amount of soda acids and heavy metal wastewater thereby in the process, is not
A kind of recovery method of green, is not suitable for industrial production.
It can be led to the problem of using the technology of vacuum metallurgy to avoid above-mentioned hydrometallurgical technology, however about vacuum metallurgy
Apparatus report it is also fewer at present, mainly have：
CN105817461A discloses a kind of device of waste and old circuit board electronic component high added value recycling, including true
Empty heating device, several concatenated condenser, holding vessel, vacuum pump, gas bottles, by sending broken electronic component
Enter in device by vacuum pyrolysis and vacuum metallurgy, make wherein nonmetallic pyrolysis, Metal gasification, by fractional condensaion by they
Separation achievees the purpose that recycling.This device is easy to operate and environmentally protective, however, on the one hand, recycling of this device for metal
Describe less, within the condenser, metal recovery work is difficult to carry out the attachment of the metal of condensation of gasifying；On the other hand, oils is condensed
With metal in the same condensing unit, and different substances cannot be distinguished according to temperature, the metal and oils being recovered to are equal
For admixture, recycling is further purified.Therefore it needs to be further improved on the basis of the present apparatus,
To further decrease the value of recovery difficult and recovery product.
Therefore, in order to efficiently recycle the metal resource in solar panels, and it is reduced to the greatest extent in removal process to ring
It is injured caused by border, is badly in need of a kind of efficient, environmental protection and the recyclable device convenient for promoting.
Summary of the invention
It is an object of the invention to provide one kind in place of overcome the deficiencies in the prior art to recycle from waste and old solar panels
The device of metal and energy gas realizes the green reclaim of metal and energy gas in waste and old solar panels, solves existing skill
Metal is difficult to the problem of separating and recycling in art.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of device recycling metal and energy gas from waste and old solar panels, including multi-temperature zone vacuum heater 1,
Alundum tube 2, assembled crucible 3, vacuum pump 4 and gas bottle 5；Multi-temperature zone vacuum heater 1 is equipped with multiple along furnace body horizontal direction
Warm area is heated, is realized by the temperature control of different heating warm area and temperature gradient variation is presented in the horizontal direction；The corundum
Pipe 2 is placed in multi-temperature zone vacuum heater 1, and assembled crucible 3 is placed in alundum tube, and assembled crucible 3 is by several crucible bases
Assembly is formed, and each crucible base corresponds to the position placement of the different heating warm area of multi-temperature zone vacuum heater 1；Alundum tube
Entrance be equipped with sealing cover A6, sealing cover A6 be equipped with atmospheric pipe 12, atmospheric pipe 12 be equipped with vent valve 8, alundum tube 2 go out
Mouth is equipped with sealing cover B7, and sealing cover B7 is equipped with the gas-guide tube 13 connecting with vacuum pump 4, and gas-guide tube 13 is equipped with vacuum pump valve 9, very
The gas outlet of sky pump 4 is connect by conveyance conduit 14 with gas bottle 5, and outlet pipe 15 and bottle valve 11 are equipped in conveyance conduit,
Outlet pipe 15 is equipped with air outlet valve 10.
The device recycles metal and energy gas by the way of vacuum cracking and vacuum metallurgy, can classify and recycle the sun
Metallic product in energy plate solves the problems, such as that hydrometallurgical process technology and equipment generates a large amount of waste water, improves existing true
Metal that empty metallurgical technology is recovered to is easy mixing, it is difficult to the problem of separation and recycling, and by the organic component in solar panels
It is converted into secondary energy sources to utilize again, the device of the invention has easy to operate, high efficiente callback, environmental-friendly feature.
Preferably, the multi-temperature zone vacuum heater 1 is equipped with 9 heating warm areas, heats the maximum temperature difference of warm area
It is 1400 DEG C, 1000 DEG C, 800 DEG C, 600 DEG C, 500 DEG C, 400 DEG C, 300 DEG C, 200 DEG C, 100 DEG C.
Preferably, the multi-temperature zone vacuum heater 1 is internally provided with thermocouple.
Preferably, the multi-temperature zone vacuum heater 1 is heated using Si-Mo rod resistance, the Si-Mo rod resistance ring
It is wound on 2 outside of alundum tube.
Preferably, vacuum meter 20 is provided on the gas-guide tube 13.
Preferably, assembled combination is carried out using concave-convex complementary form between the front end with end of the crucible base.
The binding site of each crucible base is combined by the way of concave-convex complementation, forms complete assembled crucible.
It can be prevented during heating to be difficult to collect on metal vapor condensation to corundum tube wall, assembled crucible convenient disassembly, easily
It is collected respectively in by the product of different temperature zones.
Preferably, the assembled crucible 3 is cylindrical assembled crucible.
The shape of cylindrical assembly crucible matches with corundum tube shape, can make full use of the space in alundum tube.
Preferably, the assembled crucible 3 is using graphite as material.
Graphite crucible quality is soft, high temperature resistant and can conduct heat, convenient for scraping the metal condensed on sidewall of crucible.
Preferably, the pipeline is using stainless steel as material.
Preferably, each heating warm area of the multi-temperature zone vacuum heater 1 is individually equipped with temperature control display dress
Set 17.
Temperature controls display device according to the thermocouple that heated zones in multi-temperature zone vacuum heater are arranged to judge temperature
Whether degree reaches setting value, if reaching, provides soak voltage, if not up to, bigger heating voltage is provided, if being more than
, then voltage is not provided.
It is highly preferred that the junction of the pipeline and sealing cover uses heat resistant rubber circle to seal, whole device is improved
Airtightness.
Preferably, the sealing cover is by screw detachable cover together in the inlet and/or exit of alundum tube.
The principle of the device of the invention is mainly：
(1) in the case where high temperature, vacuum, solid organic polymer can be cracked, the chemical bond of the molecule of long-chain
It is interrupted, and generates the liquid state organics of short chain and the gaseous organic substance of small molecule, liquid state organics are in the case of a high temperature by gas
Change, mobile by the temperature section of vacuum pump acted on backward, strand continues to be broken in moving process, until all becoming small
The organic gas of molecule is taken out of by vacuum pump into collection steel cylinder；
(2) principle reduced using the boiling point of metal under vacuum condition, makes metal gasify at relatively low temperature, and
It is mobile from high temperature section to low-temperature zone under vacuum pumping action, when by its condensation temperature section, then condense in the earthenware of the temperature section
On crucible wall, to be collected, using the condensation temperature difference of different metal, the present apparatus can be in the assembled earthenware of different temperature sections
It is collected into different types of metal in crucible, has also achieved the purpose that classification recycling metal simultaneously in this way.
The device of the invention system has the characteristics that following obvious：
(1) two processes of vacuum metallurgy and organic matter Pintsch process are carried out simultaneously using the same equipment, enormously simplified
The operating process of pyrometallurgy, has saved the energy.
(2) difference for utilizing different metal condensation temperature under vacuum condition system, by different metals in different temperatures rank
The position separation of section, has reached the method for being precisely separated dissimilar metals.
(3) organic component, nonmetallic inorganic component and the metal component in solar panels are separated, and there will be unit
Divide and be converted into energy gas, converts the silicon raw material of industry for nonmetallic inorganic component (silicon and silica).
Compared with prior art, beneficial effects of the present invention are：
Various different types of metal lists are finally separately recovered using waste and old solar panels as raw material in the device of the invention
Matter, pyrolysis combustion gas and silicon materials realize fine separation, recycling and the resource utilization of waste and old solar panels each component, and
Simple process, recovery efficiency is high, the discharge of object without secondary pollution, has significant economic benefit and environmental benefit.
In addition, the treatment conditions of apparatus of the present invention are vacuum, the boiling point of each component is lowered, and can greatly reduce energy consumption,
It can be oxidized simultaneously to avoid material, product will not be contaminated, and metal and nonmetallic height are additional in realizing waste and old solar panels
On the basis of value recycling, it is provided simultaneously with efficient and environmental-friendly advantage.
Detailed description of the invention
Fig. 1 is the structural representation of the device described in embodiment 1 that metal and energy gas are recycled from waste and old solar panels
Figure.
Fig. 2 is the structural representation of the device as described in example 2 that metal and energy gas are recycled from waste and old solar panels
Figure.
Fig. 3 is the design drawing and connecting method schematic diagram of assembled crucible of the invention.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to the present invention
It further illustrates.It will be appreciated by those skilled in the art that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
In embodiment, used experimental method is conventional method unless otherwise specified, material etc. used, such as nothing
Specified otherwise is commercially available.
Embodiment 1
As a kind of embodiment of the device of the present invention for recycling metal and energy gas from waste and old solar panels,
As shown in Figure 1, the device of metal and energy gas is recycled described in the present embodiment from waste and old solar panels, including multi-temperature zone is true
Empty heating device 1, alundum tube 2, assembled crucible 3, vacuum pump 4 and gas bottle 5；Multi-temperature zone vacuum heater 1 is along furnace body level
Direction is equipped with multiple heating warm areas, realizes that temperature gradient is presented in the horizontal direction to be become by the temperature control of different heating warm area
Change；The alundum tube 2 is placed in as Heated container in multi-temperature zone vacuum heater, and assembled crucible 3 is placed in alundum tube, assembled
Crucible 3 is formed by several crucible base assembly, and each crucible base corresponds to the different heating of multi-temperature zone vacuum heater 1
It places the position of warm area；The entrance of alundum tube 2 is equipped with sealing cover A6, and sealing cover A6 is equipped with atmospheric pipe 12, atmospheric pipe 12
Equipped with vent valve 8, the outlet of alundum tube 2 is equipped with sealing cover B7, and sealing cover B7 is equipped with the gas-guide tube 13 connecting with vacuum pump 4,
Gas-guide tube 13 is equipped with vacuum pump valve 9, and the gas outlet of vacuum pump 4 is connect by conveyance conduit 14 with gas bottle 5, in conveyance conduit 14
Equipped with outlet pipe 15 and bottle valve 11, outlet pipe 15 is equipped with air outlet valve 10.
Embodiment 2
As a kind of embodiment of the device of the present invention for recycling metal and energy gas from waste and old solar panels,
As shown in figures 2-3, the device of metal and energy gas is recycled described in the present embodiment from waste and old solar panels, including mostly warm
Area's vacuum heater 1, alundum tube 2, assembled crucible 3, vacuum pump 4 and gas bottle 5；Multi-temperature zone vacuum heater 1 is along furnace body
Horizontal direction is equipped with multiple heating warm areas, is realized by the temperature control of different heating warm area and temperature ladder is presented in the horizontal direction
Degree variation；The multi-temperature zone vacuum heater 1 is equipped with 9 heating warm areas, the maximum temperature for heating warm area is respectively 1400 DEG C,
1000℃,800℃,600℃,500℃,400℃,300℃,200℃,100℃；The alundum tube 2 is placed in multi-temperature zone vacuum and adds
Heated container is used as in thermal 1, assembled crucible 3 is placed in alundum tube 2, and assembled crucible 3 is formed by 9 crucible base assembly,
And each crucible base corresponds to the position placement of the different heating warm area of multi-temperature zone vacuum heater；The entrance of alundum tube 2 is set
There are sealing cover A6, sealing cover A6 to be equipped with atmospheric pipe 12, atmospheric pipe 12 is equipped with vent valve 8, and the outlet of alundum tube 2 is equipped with close
B7 is covered, sealing cover B7 is equipped with the gas-guide tube 13 connecting with vacuum pump 4, and gas-guide tube 13 is equipped with vacuum pump valve 9, vacuum pump 4
Gas outlet is connect by conveyance conduit 14 with gas bottle 5, and outlet pipe 15 and bottle valve 11, escape pipe are equipped in conveyance conduit 14
Road 15 is equipped with air outlet valve 10.
Preferably, the multi-temperature zone vacuum heater 1 is internally provided with thermocouple.
Preferably, the multi-temperature zone vacuum heater 1 is heated using Si-Mo rod resistance 16, the Si-Mo rod resistance
16 are looped around 2 outside of alundum tube.
Si-Mo rod distribution of resistance with thermocouple is looped around on the outside of alundum tube in each inner wall for heating warm area.
Each heating warm area independent heating, independent thermometric, independent control are controlled by the temperature of different heating warm area and are realized
Temperature gradient variation is presented in the horizontal direction.
Preferably, vacuum meter 20 is provided on the gas-guide tube 13.
Preferably, assembled combination is carried out using concave-convex complementary form between the front end with end of the crucible base.Respectively
The binding site of a crucible base is combined by the way of concave-convex complementation, the complete assembled crucible of formation, convenient disassembly, easily
In the recovery product for collecting different temperature zones.
Preferably, the assembled crucible 3 is cylindrical assembled crucible.
The shape of cylindrical assembly crucible matches with corundum tube shape, can make full use of the space in alundum tube.
It is further preferred that as shown in figure 3, the crucible base is hollow cylinder 32, the front end of hollow cylinder
It is designed using recess, is equipped with nested cylinder ring 31, the outer diameter of nested cylinder ring is corresponding to the internal diameter of hollow cylinder end.Crucible
Matrix uses the design of size bicylindrical shape, splices to front and back, can prevent metal vapor condensation to just during heating
It is difficult to collect so as to cause metal on beautiful tube wall, and assembled crucible convenient disassembly, facilitates the product for collecting different temperature zones.
Preferably, the assembled crucible 3 is using graphite as material, and graphite crucible quality is soft, high temperature resistant and can conduct heat,
Convenient for the metal condensed on sidewall of crucible is scraped.
Preferably, the pipeline is the organic gas corrosion pipeline prevented using stainless steel as material in product.
It is further preferred that the gas bottle 5 uses stainless steel gas bottle, prevent organic gas from corroding.
Preferably, each heating warm area of the multi-temperature zone vacuum heater 1 is individually equipped with temperature control display dress
Set 17.
Temperature controls display device according to the thermocouple that heated zones in multi-temperature zone vacuum heater are arranged to judge temperature
Whether degree reaches setting value, if reaching, provides soak voltage, if not up to, bigger heating voltage is provided, if being more than
, then voltage is not provided.
Preferably, the junction of the pipeline and sealing cover uses heat resistant rubber circle to seal, to guarantee whole device
Airtightness.
Preferably, the sealing cover is by screw detachable cover together in the inlet and/or exit of alundum tube.
Preferably, the multi-temperature zone vacuum heater uses multi-temperature zone electron tubes type high temperature furnace.
A kind of operating method for the device that metal and energy gas are recycled from waste and old solar panels of embodiment 3
The device operating method of recycling metal and energy gas from waste and old solar panels of the invention includes the following steps：
(1) the solar energy electroplax material after shearing-crushing is placed in from corundum tube inlet meter first crucible base,
Multiple crucible bases are connected to form the position that assembled crucible 3 is placed in alundum tube 2 and corresponds to different heating warm areas, even
Each section is connected, and closes vent valve 8, bottle valve 11, opens air outlet valve 10, vacuum pump valve 9, opens vacuum pump 4；
(2) when the vacuum degree on gas-guide tube 13 is less than 10Pa, air outlet valve 10 is closed, and open bottle valve 11, set respectively
The heating parameter of multi-temperature zone vacuum heater 1 is set, wherein the temperature highest of the corresponding heating temperature of first crucible base,
The temperature of subsequent heating warm area successively reduces, and after the crucible base without material is warming up to the temperature of setting, then opens
It opens first heating warm area to heat material, the residence time is no less than 2h；
(3) after stopping heating, bottle valve 11 and vacuum pump 4 are closed, room temperature is cooled to in-furnace temperature, opens vent valve 8
Make pressure recovery atmospheric pressure in alundum tube 2, and take out assembled crucible 3, metal and silicon product are collected from each crucible base, and
Fuel gas is collected into gas bottle 5.
The principle of the device of the invention is mainly：
(1) in the case where high temperature, vacuum, solid organic polymer can be cracked in waste and old solar panels, long-chain
Molecular chemical bond be interrupted and generate the liquid state organics of short chain and the gaseous organic substance of small molecule, liquid state organics are in high temperature
In the case of gasified, and mobile toward low-temperature zone by the effect of vacuum pump, strand continues to be broken in moving process, until whole
The organic gas for becoming small molecule, is taken out of by vacuum pump into gas bottle；
(2) principle reduced using the boiling point of metal under vacuum condition, makes metal gasify at relatively low temperature, and
It is mobile from high temperature section to low-temperature zone under vacuum pumping action, when by its condensation temperature section, then condense in the earthenware of the temperature section
On crucible wall, to be collected, using the condensation temperature difference of different metal, the present apparatus can be in the assembled earthenware of different temperature sections
It is collected into different types of metal in crucible, has also achieved the purpose that classification recycling metal simultaneously in this way.
In device heating process, first the temperature liter of the corresponding heating warm area setting of no crucible base that material is added
Up, form it into a temperature gradient, in this way in order to be heated to material when the gaseous metal that is formed and organic
Object is directly entered temperature gradient, achievees the effect that separation and recovery.
During heating as much as possible by vacuum degree control in lower level, can be combined using prime mechanical pump true
The system of empty diffusion pump carries out the holding of vacuum degree, can achieve 10~2Pa in this way, even lower, according to gram of perfect gas
Lao Xiusi-Clapeyron equation, vacuum pressure is lower, and the boiling point of liquid is lower, and lower maximum temperature can be set in this way,
To achieve the purpose that reduce energy consumption.
Embodiment 4 recycles the application example of metal and energy gas from waste and old solar panels
The recycling of metal and energy gas in waste and old solar panels is carried out using the device of embodiment 2.
Waste and old solar panels are subjected to shearing-crushing 20min first, until obtaining fragment that diameter is 10mm or so and big
Comminuted powder is measured, average grain diameter is 50 μm, is subsequently placed in crucible base, in addition takes 8 same crucible bases, will fill solar energy
As first crucible base, remaining is successively stitched together to form assembled crucible 3 crucible base of plate material 19, then will spell
Dress crucible 3 is placed in alundum tube 2, wherein first crucible base corresponds to level-one heating warm area, second crucible base corresponding two
Grade heating warm area, third crucible base correspond to three-level heat warm area, the 4th crucible base correspond to level Four heat warm area, the 5th
A crucible base corresponds to Pyatyi heating warm area, the corresponding six grades of heating warm areas of the 6th crucible base, and the 7th crucible base corresponds to
Seven grades of heating warm areas, the corresponding eight grades of heating warm areas of the 8th crucible base, the corresponding nine grades of heating warm areas of the 9th crucible base are put
It sets, connects multi-temperature zone vacuum heater 1, vacuum pump 4 and gas bottle 5, and close vent valve 8, bottle valve 11, open outlet
Valve 10, vacuum pump valve 9 open vacuum pump, when the vacuum meter 20 on gas-guide tube shows that pressure is less than 10Pa, close air outlet valve
10, and bottle valve 11 is opened, the heating parameter of 9 warm areas of a lot of warm area vacuum heaters 1 is set separately, including when heating
Between, maximum temperature and residence time, wherein the temperature highest of the corresponding heating warm area of first crucible, level-one heat warm area most
High-temperature is 1400 DEG C, and the maximum temperature that second level heats warm area is 1000 DEG C, and the maximum temperature that three-level heats warm area is 800 DEG C,
The maximum temperature that level Four heats warm area is 600 DEG C, and the maximum temperature that Pyatyi heats warm area is 500 DEG C, and six grades of heating warm areas are most
High-temperature be 400 DEG C, seven grades heating warm areas maximum temperatures be 300 DEG C, eight grades heating warm areas maximum temperatures be 200 DEG C, nine
The maximum temperature of grade heating warm area is 100 DEG C, is then turned on level-one after two to eight grades of heating warm areas reach the temperature of setting and adds
Hot warm area heats material, residence time 2.5h.After to be heated, heating system, bottle valve 11 and vacuum are closed
Pump 4 is cooled to room temperature to in-furnace temperature, and opening vent valve 8 makes pressure in alundum tube 2 return back to atmospheric pressure, takes out assembled crucible
3, and it is collected into from 1400 DEG C of crucible base the SiO of fragment2And Si, and in the not same district of lower temperature (within 500 DEG C)
The metal powder of Cu, Se, In, Ga are scraped respectively on the crucible base wall of section, and are collected into from gas bottle and be can be used as the energy
Small molecule organic gas.The short chain gas collected finds only to can be used as fuel gas after compression containing C, H, O element after testing
Body can be used as secondary energy sources use.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (9)
1. a kind of device for recycling metal and energy gas from waste and old solar panels, which is characterized in that including multi-temperature zone vacuum
Heating device (1), alundum tube (2), assembled crucible (3), vacuum pump (4) and gas bottle (5)；Multi-temperature zone vacuum heater (1)
Multiple heating warm areas are equipped with along furnace body horizontal direction, is realized by the temperature control of different heating warm area and is presented in the horizontal direction
Temperature gradient variation；The alundum tube (2) is placed in multi-temperature zone vacuum heater (1), and assembled crucible (3) is placed in alundum tube
(2) in, assembled crucible (3) is formed by several crucible base assembly, and each crucible base corresponds to multi-temperature zone heating in vacuum dress
It places the position for setting the different heating warm area of (1)；The entrance of alundum tube (2) is equipped with sealing cover A (6), and sealing cover A (6) is equipped with
Atmospheric pipe (12), atmospheric pipe (12) are equipped with vent valve (8), and the outlet of alundum tube (2) is equipped with sealing cover B (7), sealing cover B
(7) it is equipped with the gas-guide tube (13) connecting with vacuum pump (4), gas-guide tube (13) is equipped with vacuum pump valve (9), and vacuum pump (4) goes out
Port is connect by conveyance conduit (14) with gas bottle (5), and outlet pipe (15) and bottle valve are equipped in conveyance conduit (14)
(11), air outlet valve (10) are equipped in outlet pipe (15).
2. the device according to claim 1 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
The multi-temperature zone vacuum heater (1) is equipped with 9 heating warm areas, and the maximum temperature for heating warm area is respectively 1400 DEG C, 1000
℃、800℃、600℃、500℃、400℃、300℃、200℃、100℃。
3. the device according to claim 1 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
The multi-temperature zone vacuum heater (1) is internally provided with thermocouple.
4. the device according to claim 1 or 3 for recycling metal and energy gas from waste and old solar panels, feature exist
In the multi-temperature zone vacuum heater (1) is heated using Si-Mo rod resistance, and the Si-Mo rod resistance is looped around alundum tube
(2) outside.
5. the device according to claim 1 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
The gas-guide tube (13) is provided with vacuum meter (20).
6. the device according to claim 1 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
Assembled combination is carried out using concave-convex complementary form between the front end of the crucible base and end.
7. the device according to claim 6 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
The assembly crucible (3) is cylindrical assembled crucible.
8. the device according to claim 1 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
The pipeline is using stainless steel as material, and the assembly crucible (3) is using graphite as material.
9. the device according to claim 1 for recycling metal and energy gas from waste and old solar panels, which is characterized in that
Each heating warm area of the multi-temperature zone vacuum heater (1) is individually equipped with temperature control display device (17).
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| CN201810598131.2A CN108913899A (en) | 2018-06-11 | 2018-06-11 | A kind of device recycling metal and energy gas from waste and old solar panels |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019679A (en) * | 2019-12-13 | 2020-04-17 | 中山大学 | Device for recovering energy substances from hyper-enriched plants and application thereof |
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| CN85100107A (en) * | 1985-04-01 | 1986-07-30 | 清华大学 | The vacuum distillation plant that vaporization and condensation combines |
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Application publication date: 20181130 |