EP4259408A1 - Plastics and glass recovery from end-of-life photovoltaic panels - Google Patents
Plastics and glass recovery from end-of-life photovoltaic panelsInfo
- Publication number
- EP4259408A1 EP4259408A1 EP21835837.2A EP21835837A EP4259408A1 EP 4259408 A1 EP4259408 A1 EP 4259408A1 EP 21835837 A EP21835837 A EP 21835837A EP 4259408 A1 EP4259408 A1 EP 4259408A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plastics
- glass
- recovery
- treatment
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 107
- 229920003023 plastic Polymers 0.000 title claims abstract description 107
- 239000004033 plastic Substances 0.000 title claims abstract description 107
- 238000011084 recovery Methods 0.000 title claims abstract description 66
- 206010011906 Death Diseases 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 239000002184 metal Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 65
- 238000011282 treatment Methods 0.000 claims abstract description 61
- 150000002739 metals Chemical class 0.000 claims abstract description 50
- 239000000853 adhesive Substances 0.000 claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims description 54
- 238000000926 separation method Methods 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 239000003292 glue Substances 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000002386 leaching Methods 0.000 claims description 17
- 239000004568 cement Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000010426 asphalt Substances 0.000 claims description 6
- 150000004679 hydroxides Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 239000011669 selenium Substances 0.000 claims description 6
- 230000007928 solubilization Effects 0.000 claims description 6
- 238000005063 solubilization Methods 0.000 claims description 6
- 230000001464 adherent effect Effects 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000008121 dextrose Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- -1 fluorinated Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000003381 solubilizing effect Effects 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000965 Duroplast Polymers 0.000 claims description 3
- 239000004638 Duroplast Substances 0.000 claims description 3
- 230000003667 anti-reflective effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 239000010882 bottom ash Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000021962 pH elevation Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229920000426 Microplastic Polymers 0.000 claims 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000005038 ethylene vinyl acetate Substances 0.000 claims 1
- 239000012454 non-polar solvent Substances 0.000 claims 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 15
- 239000002609 medium Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 238000004064 recycling Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000005337 ground glass Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000009996 mechanical pre-treatment Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000007237 Aegopodium podagraria Nutrition 0.000 description 1
- 244000045410 Aegopodium podagraria Species 0.000 description 1
- 235000014429 Angelica sylvestris Nutrition 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001251094 Formica Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 208000034809 Product contamination Diseases 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910034327 TiC Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JXPACFZBLKPSRP-UHFFFAOYSA-N pentane;hydrate Chemical compound O.CCCCC JXPACFZBLKPSRP-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/50—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/75—Plastic waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0217—Mechanical separating techniques; devices therefor
- B29B2017/0237—Mechanical separating techniques; devices therefor using density difference
- B29B2017/0244—Mechanical separating techniques; devices therefor using density difference in liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
-
- 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
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention refers to the recovery of plastics and glass from photovoltaic panels at the end of their life.
- the invention also includes the recovery of the metals present in said panels.
- the recycling of solar panels has gradually become an important environmental issue not only for the metals they contain, largely made up of heavy metals (lead, tin and cadmium) but also because the incorrect treatment of these waste involves a large production of waste whose destiny is to landfill.
- the recovery processes are particularly focused on the enhancement of the metals of the solar cells and little has been done on the recovery of the glassy part, which instead constitutes about 70% of the panel and which is often recovered with ineffective techniques or remains as a degraded part in metal recovery processes and is disposed of as waste. Instead, it should be emphasized that the glass used in solar panels is a material with a high added value.
- cement glass has a value close to € O/ton
- common recycling glass has a value of approximately € 52/ton (Recycling - secondary material price indicator, Eurostat, Source: Statistics Explained (htl s:Z/eo,eurQpa ⁇ eu/eurQS at/sta istjCsexpfeined/) - 21/10/2020) while solar glass for panels has an economically high value that exceeds> 100 €/ton (recycled crushed glass, Facebook).
- only the latter type of glass can be used for glass containers in the food or cosmetic industry or to create new solar panels.
- Some techniques involve processing the entire panel without first carrying out specific mechanical pre-treatments and these processes are highly disadvantageous above all because they involve a considerable waste of reagents and reduced efficiency since the solvent/panel contact surface is not maximized, thus preventing detachment of the glue from the glass.
- the immersion of the entire panel does not allow the optimal separation of the components and therefore implies their reuse as materials with low added value (for instance the cement market). If mechanical pre-treatments are carried out, a suitable particle size separation of the fractions aimed to the downstream recovery processes is not carried out.
- the solvent consists of gas in supercritical conditions (for instance CO2 fed between 50 and 500 bar).
- Patent EP 2997169 deals with the recovery of solar panels at the end of their life, but is focused on the recovery of metals and does not provide useful lessons with regard to the recovery of glass and plastics.
- the intermediate fraction (0.1 -1 mm) is considered to be made up of clean, directly reusable glass; however it contains impurities (plastics and metals) and is difficult to market due to the size as it is too fine. It is therefore not usable as solar glass and is also given to cement factories, although lately even this use is no longer suitable due to the presence of contaminating residual metals;
- the glass fraction recovered will be contaminated by these metal filaments.
- a heat treatment of the coarse fraction is proposed, which however has the disadvantage of opacifying the glass and burning the fluorinated compounds which are toxic.
- Patent US10618268 describes a method for recycling the various components of photovoltaic panels by mechanical crushing to obtain three dimensional fractions, followed by washing.
- the washing is performed separately for the three fractions and is carried out in tanks with the use of a water-based fluid containing surfactants and organic solvents designed to separate light particles from larger and heavier particles, such as glass fragments.
- the separation can be carried out by filtration.
- the fine fraction will be dispersed in the liquid medium and will make separation more difficult, even contaminating the coarser products.
- the use of the surfactant component has numerous other disadvantages, in addition to that of dirtying the products being treated and creating foams on which the finer granulometry products adhere.
- the surfactant by its nature, facilitates the miscibility of all liquids, including the solvents present in the washing mixture, therefore it hinders the recovery and separation of the individual fluids, which cannot therefore be reused. This involves wastewater waste that must be properly disposed of or makes the recycling of liquid components extremely complex, preventing closed-cycle operations.
- An object of the present invention is therefore to enhance the glassy material of the photovoltaic panels at the end of their life in order to recover clean glass with the same characteristics as the original glass.
- Another object of the invention is to maximize the amount of glass to be reused as a secondary raw material and minimize the amount of glass powder (size ⁇ 1 mm) by reducing the amount to less than 10% by weight of the initial panel.
- Still another object is to enhance the plastics, separating the various types from each other so as to recover those of interest such as fluorinated ones, such as Tedlar®.
- Still further object is that of recovering the metals adhered to the adhesive plastics, and that of recovering also these plastics, which constitute the least exploitable part of the panels and which can be reused in the mixes for bitumen.
- An additional object is to treat the residual glass powder, which is sent to the chemical recovery of the metals and which, when cleaned of them, can then be sent to the cement factories without load of polluting metals.
- Figure 1 schematically illustrates a polycrystalline silicon solar panel: A) frame of aluminum or aluminum alloys; B) tempered glass; C) glue layer (for instance based on EVA (ethylene/vinyl-acetate copolymer); D) metallic element (or solar cell) based on Silicon with metals such as cadmium, selenium, tellurium, gallium, molybdenum, indium, silver, zinc etc.
- F) Junction Box which includes diodes, cables and connectors;
- FIG. 2 is a block diagram of the process
- Figure 3 is a scheme of a reactor for sink and float separation with turbulent movement of the fluid in the liquid bulk
- FIGURES 4A and 4B respectively show the results of the sink and float separation process carried out with an unsatisfactory (4A) and satisfactory (4B) medium according to the invention.
- the separation of the detached components with the previous treatment is not effective due to the unsuitability of the density of the medium used.
- the means chosen by the invention is the most effective because it allows an optimal separation of the components, as can be seen in the figure, which are positioned in different points of the vehicle;
- FIGURE 5 shows clean glass particles following the treatment object of the invention
- FIGURE 6 shows EVA particles recovered following the treatment object of the present invention
- FIGURE 7 shows clean TEDLAR® particles separated with the treatment object of the invention.
- the present invention relates to a process for the treatment of all types of mono, poly-crystalline and amorphous silicon-based photovoltaic panels and of the latest generation thin-film panels (such as the so-called CIGS (copper-based , indium, gallium, selenium) and those in kesterite which do not have the silicon cell), which can be treated together or, preferably, separately.
- CIGS copper-based , indium, gallium, selenium
- kesterite which do not have the silicon cell
- the main objective of the invention is to recover the plastics of different nature that make up the panel and the high-purity glass, thus preserving their added value, in order to be able to put them back on the market as secondary raw materials (SRM).
- SRM secondary raw materials
- the process involves a mechanical treatment of grinding and physical detachment of the adhesives from the other components (glass and other plastics) and further chemical treatments of the plastics and of the fine glass fraction for the recovery of metals in order to obtain a enhanced solid residue.
- the adhesive plastics have strong adhesive characteristics and are used in the preparation of the photovoltaic module to encapsulate the metal cell and adhere to the transparent glass, favoring the sandwich structure typical of the panels, these plastics will hereinafter also be referred to generically, but not limitedly, with the term “adhesives”.
- the process according to the invention comprises the following stages to operate on the panel, once the frame (typically aluminum or its alloys) and the electrical connections (usually junction boxes) have been eliminated:
- the process allows to reach and exceed the minimum material recovery target set by the European directive 2012/19/EU and equal to 85% by weight.
- the mechanical grinding treatment is aimed at the production of only two fractions in which the finer dimensional fraction is minimized.
- the latter is also separated from the main coarse fraction before entering the subsequent wet process stages, with the advantage of avoiding product contamination. This is advantageous in view of recovering clean glass of a coarse size with a high added value that allows it to be reused.
- the coarse fraction is treated in a reactor (typically a reactor at atmospheric pressure and low temperature, in the range T (ambient)-80°C, preferably 25-70°C, more preferably 55-65°C) with a solvent or mixture of solvents that does not solubilize plastics (the solvent will typically be an aprotic apolar solvent, such as cyclohexane, kerosene or light hydrocarbons such as hexane) in order to allow the detachment of the various components (glass, metal contacts, adhesive plastics/glues with adhered portions of metallic solar cell, other plastics, including for instance fluorinated ones); the skilled in the art will be able to find the appropriate conditions to have an efficient separation in order to have the greatest possible separation between the various elements (glass and plastics) bearing in mind that the treatment will be a physical separation treatment and will not lead to the solubilization of the plastics (in particular the adhesive plastics will only be swollen by the solvent), thanks to the chosen solvent or at
- agitation will be maintained inside the reactor through external recirculation of liquid and not through mechanical means such as blades or rotors in order not to shatter the glass.
- the recirculation will be such as to maintain an expanded bed condition within the liquid bulk in order to favor glass/plastic contact and allow the latter to remain suspended in the liquid medium.
- the solvent leaving the reactor, before being recirculated in the reactor can be subjected to filtration in order to intercept the adhesive plastics with adherent metal cell fractions possibly entrained, which will then go to hydrometallurgical recovery.
- the solvent and the conditions chosen for this stage are also effective on a coarse size which allows to separate a coarse glass which maintains its added value in its subsequent re-uses.
- the solvent is then removed to separate the liquid from the solids (for instance by drainage) while avoiding drying the solids; this operation must be quick to prevent the solids from reattaching to each other.
- the collected solvent before being reused in the next treatment cycle, can be subjected to a rectification, to maintain its purity adequate.
- the process fluids, solvent and aqueous medium do not come into contact with each other since two operations are foreseen in series and distinct from each other. Furthermore, since the two fluids are immiscible, any small contaminations do not compromise the purification of the process liquids which therefore remain easily separable thanks also to the non-use of components such as surfactants;
- water or other non-solubilizing liquid is quickly added (preferably from below) to allow the separation of the various components.
- the water or other liquid that is not miscible with the solvent of stage (iii) has the function of behaving as a dense medium and allowing a sink and float separation such as the adhesive plastics, swollen and impregnated with solvent, will tend to float, separating from the glass, metal contacts and other heavier plastics, which instead will remain on the bottom.
- the separation therefore exploits the difference in density of the components that are distributed in the dense medium.
- the choice of the specific medium of the invention allows the stratification of the light components on the free surface and the deposition of glass and heavy plastics on the bottom of the reactor (exactly at the two ends of the dense medium). Their subsequent recollection is therefore easy and efficient.
- the chosen medium water or other aqueous-based liquid that does not solubilize plastics and immiscible with the apolar aprotic solvent or solvents
- a simplified embodiment illustrated in Figure 3
- the plastics swollen with solvent are removed by skimming.
- the washing is carried out avoiding mechanical handling and moving the fluid by forced external circulation of the liquid, capable of maintaining a suitable turbulence in the liquid bulk (possibly assisted by the injection of nitrogen or inert gas).
- the glass with the metal contacts and the heavy plastics, for instance fluorinated remains as the bottom body, which is easily discharged after draining the water.
- the final product is wet only by water and not by the solvent: therefore no further washing of the products will be necessary.
- the treatment of the fraction separated with the sink and float and consisting of the adhesive plastics (type EVA) and the metals contained in the photovoltaic cell can be done by hydrometallurgical methods (with quantitative recovery of the adhesive that is reused as bitumen) or by thermal methods.
- the solvents that can be used in stage (ii) are selected from: cyclohexane, specific aprotic apolar type solvent, kerosene or light hydrocarbons with a solid/liquid ratio (S/L) in the range from 1 :1 to 1 :8 (preferably 1 :4 ).
- the liquid to be used must have an intermediate density between the plastics and the glass.
- the liquid is water which allows to proceed according to a densimetric separation and provides significant simplifications to the total process, making it also advantageous from an environmental point of view as it is an easy to find component and does not involve any environmental impact related to its production.
- the main objective of the present invention is to separate glass from plastics and plastics of different types (glue such as EVA or Duroplast (thermosetting composite plastic, similar to Formica and Bakelite htps fluorinated Tedlar® type, polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polymers based on PEDOT (poly(3,4-ethylenedioxythiophene)- polystyrene), and similar plastics, with each other through the procedure described below.
- glue such as EVA or Duroplast (thermosetting composite plastic, similar to Formica and Bakelite htps fluorinated Tedlar® type, polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polymers based on PEDOT (poly(3,4-ethylenedioxythiophene)- polystyrene), and similar plastics, with each other through the procedure described below.
- the aluminum frames are removed using a robotic/automated system that uses specific tools even when hot.
- the operation is optimized to minimize the production of glass dust and separate the uncontaminated aluminum frame from the other panel components and directly marketable to the aluminum market as SRM.
- the junction boxes are also removed.
- the frameless panel is suitably ground with a suitable and specific system, such as single-shaft grinder with anti-abrasive plates or similar, such as the GR280 grinder from CAMEC (htt s://camec.net/divisioni/divisione- capable of minimizing the minute fraction to the advantage of the production of a coarse-sized fraction and equipped with a 20 mm control grid.
- a suitable and specific system such as single-shaft grinder with anti-abrasive plates or similar, such as the GR280 grinder from CAMEC (htt s://camec.net/divisioni/divisione- capable of minimizing the minute fraction to the advantage of the production of a coarse-sized fraction and equipped with a 20 mm control grid.
- the shredded product is then screened using a 1 mm sieve to separate two particle size fractions:
- a fine fraction ( ⁇ 1 mm) consisting of a concentrate of metals and residues of glass dust and traces of plastics.
- the metal contacts (tin, lead, aluminum and other filaments) released during grinding are preliminarily separated from the coarse fraction by means of an optical system or the like.
- PHYSICAL TREATMENT Only the so cleaned ⁇ coarse fraction is sent to the physical treatment which consists of a wet treatment with a specific apolar aprotic solvent such as cyclohexane or kerosene or light hydrocarbons for the detachment of the glue (for instance EVA) from the glass.
- a specific apolar aprotic solvent such as cyclohexane or kerosene or light hydrocarbons
- An S/L ratio is used in the range from 1 :1 to 1 :8 (preferably 1 :4) at a temperature between the Tambient - 80°C (preferably 65°C) and for an overall duration of the process comprised in the range 0.5-4 hours (preferably 2 hours). Agitation is maintained with forced external recirculation of liquid.
- a "sink and float" separation is then carried out in an appropriate liquid/thick medium which will have a density in the range 2-0.7 g/cm 3 measured under standard conditions (for instance water or other nonsolubilizing liquid as mentioned above), or between that of the glass and the suspended polymeric elements.
- the treatment will be carried out at a temperature comprised in the range Tambient - 70°C (preferably 35°C) for the separation of two fractions: 1 ) glass with metal contacts and heavy plastic (for instance fluorinated such as Tedlar®) and 2) adhesive plastic (for instance EVA) with the photovoltaic cell attached.
- a flow of inert gas such as nitrogen
- inert gas such as nitrogen
- a quantity between 10-50 nitrogen vol./reactor vol. can be used at a pressure between 1.1 -5 bar to assist the separation or preferably an external forced circulation of the dense medium will be implemented to minimize the use of inert gas.
- the subsequent separation of the glass from the fluorinated compound can be achieved with air blow or zig zag separators.
- the subsequent separation of the metal contacts from the glass can be achieved with an optical system.
- the fine fraction is fed to a chemical treatment of the hydrometallurgical type for the recovery of the metals concentrated therein.
- the sequential chemical washing for the recovery of metals and silicon can take place in one of the following ways: • Basic leaching at pH 12-14, particularly advantageous for silicon- based panels, using NaOH (0.5 M), for the selective extraction of Al and Zn. This operation is carried out at 80°C for 5h. Subsequently the lye is filtered thus obtaining a solid cake and a leach liquor:
- the solid cake undergoes acid leaching with H2SO4 (2.5 M) for the removal of Fe and thus leading to obtaining a solid residue consisting of TiC and Ag, clean minute glass and traces of glue (for instance EVA).
- H2SO4 2.5 M
- This operation is carried out at 40°C for 5 h.
- This solid fraction is treated with HNO3 (25% w) for the solubilization of residual silver and zinc, at a temperature in the range 40-80°C (preferably 60°C), for a duration of 2-4 h with a liquid/solid (L/S) ratio of 3 to 5 (preferably 4.6).
- HCI is then added to precipitate the silver in the chloride form.
- the precipitate is washed until any impurities (zinc, iron) are eliminated and then chemically reduced with caustic soda and dextrose.
- the silver is then washed with demineralized water and finally placed in an oven at about 300°C for a few hours after adding sodium bicarbonate. Finally it is melted in a well-type oven.
- the solid residue can be reused in cement factories.
- the solids are separated with a filter press or centrifuge.
- the leach liquor after filtration contains mainly Zn and is subjected to recovery by precipitation as hydroxide, carried out by adding alkaline agents at pH 10-11 , or electrochemically, possible only after the previous purification operations.
- the residual solid containing glass, Si, Ag, TiO2 and traces of glue can be reused in the production of Si, Ag and Ti.
- This solid fraction is treated with HNO3 (25% w) for the solubilization of silver and residual zinc, at a temperature in the range 40-80°C (preferably 60°C), for 2-4 h with a liquid/solid (L/S) ratio of 3 to 5 (preferably 4.6).
- HCI is then added to precipitate silver in the form of chloride.
- the precipitate is washed until any impurities (zinc, iron) are eliminated and then chemically reduced with caustic soda and dextrose.
- the silver is then washed with demineralized water and finally placed in an oven at about 300°C for a few hours after adding sodium bicarbonate. Finally it is melted in a well-type oven.
- the solid residue can be reused in cement factories.
- the solid cake is made up of a residue of SiO2, glass and traces of glue (for instance EVA).
- Patent EP 2997169 deals with the recovery of metals from solar panels at the end of their life. Unlike the proposed processes, this patent operates a sequential alkaline leaching by using soda at a high concentration (10M) to recover Al and Zn.
- the fraction consisting of glue impregnated with solvent adhered to the photovoltaic cell will first be dried to remove and recover the solvent that impregnates the glue.
- a leaching is carried out directly in the same ways as already described in the treatment of the fine fraction.
- the metals are recovered from the lye while the residual solid, sufficiently decontaminated by the metals, consisting of the glue granules (for instance EVA) is recovered and can be reused for instance in the bitumen market.
- the glue granules for instance EVA
- an incineration of the glue with the adhered cell is carried out between 500 and 700°C for 2-5 hours, preferably 650°C for 4 hours.
- the process works mainly in a closed cycle with the minimization of the waste produced.
- the solvent can be reused after refining.
- the quantities of reagents used are minimized and can be reused for a defined number of cycles. This is favored by the non-miscibility of the process liquids (solvents and aqueous phase) and their not expected mixing during the process.
- the solvent chosen for the separation is effective even on a coarse size. This is advantageous in view of recovering coarsesized glass with high added value.
- the grinding is targeted and designed in a specific way: it is aimed at producing a particle size fraction shifted towards high (not fine) sizes to obtain a product (glass) with high added value (without compromising the qualities of a flat and transparent material) and with a size such as to be reused in sectors such as glassworks for the food and cosmetic industry for which it is resalable at a higher value than e.g. to cement factories (for which a fine size is sufficient).
- the 1 mm granulometric fraction satisfies the requests of the end-users of the recovered product.
- Controlled grinding also allows the metal fraction to be concentrated in a specific dimensional range (0-1 mm) and therefore avoids chemical treating of other portions of the panel in which these metals are not present for the recovery of target metals (with an unavoidable dilution effect of metals in the sample leading to lower recovery efficiency).
- the main advantage of the invention is the separation of four distinct and uncontaminated streams: glass, metal contacts, glue (for instance EVA) and plastic (for instance fluorinated such as Tedlar®).
- the proposed separation makes it possible to recover these fractions while preserving their added value so that they can be reintroduced directly into the market as SRM. In fact, they are recovered with the following degrees of purity: glass >99%, glue (EVA type) >95%, plastic (for instance fluorinated type Tedlar®) >95%, metal contacts >99%.
- the reference target for recovered glass is, for instance, that of glass factories where flat glass with high added value is used. This purity level is also achieved through the use of refining stages, such as the separation of metal contacts from glass by means of an optical separator.
- the solvents to be used, object of the invention are of the apolar aprotic non-carcinogenic type, kerosene and light hydrocarbons.
- the use of solvents with reduced volatility for instance less than acetone
- cyclohexane will be preferred which, in addition to not being carcinogenic, is 100% recyclable, an aspect that constitutes an additional added value: its recovery and re-use in the closed-cycle process avoids its disposal with minimization of the environmental impact.
- Mechanical agitation is completely eliminated both in the solvent treatment and during the "sink and float" separation: the separation is more efficient by fluid dynamics (through an external forced circulation of liquid that is reintroduced into the reactor) which favors solvent/panel flakes contact.
- the mechanical stirring system constitutes an obstacle to the correct fluid dynamics of the system and causes (even if weak) an unavoidable breakage of the glass.
- the process conditions are not difficult for the separation of the glass from the glue (for instance EVA) and from the polymer (for instance fluorinated Tedlar type) and gases (such as CO2) are not used in supercritical conditions.
- Working with gas in supercritical conditions implies very high operating pressures: this involves the creation of a complex compression and expansion system (with obvious economic burden).
- the proposed solvent treatment and sink and float separation temperatures are such that they do not involve an economic burden for a possible industrial application of the process (a heating boiler and a simple vapor condensation system would be sufficient).
- the times are such as to allow numerous processing cycles per day to maximize the processed panels and the recovered product.
- the solvent treatment temperature is optimized to minimize operating times without however causing excessive solvent evaporation: a temperature that is too high, due to the volatility of the solvents, in fact, would lead to a loss which would lead to the need to use recovery which entails an increase from an economic point of view.
- a "sink and float" separation of the wet detached components is carried out, which allows the optimal recovery of uncontaminated fractions. This separation also allows the different types of plastics to be optimally separated from each other.
- the application advantage which represents a chemical improvement of the process, is to feed to the chemical treatment only the fraction of interest, wherein are concentrated metals more easily recoverable through hydrometallurgical processes.
- a mechanical concentration is achieved (thanks to the optimization of the specific grinding and screening stage) which results in a much smaller quantity of sample to be treated.
- the whole process from the robotic/automated dismantling to the final chemical treatment, aims to maximize the recovery of material by recovering pure components that can be placed directly on the market as SRM.
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Abstract
Description
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IT102020000030176A IT202000030176A1 (en) | 2020-12-09 | 2020-12-09 | RECOVERY OF PLASTIC AND GLASS FROM END OF LIFE PHOTOVOLTAIC PANELS |
PCT/IB2021/061419 WO2022123444A1 (en) | 2020-12-09 | 2021-12-07 | Plastics and glass recovery from end-of-life photovoltaic panels |
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CN115365256A (en) * | 2022-08-10 | 2022-11-22 | 安徽光智科技有限公司 | Method for repairing optical lens |
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ITRM20130286A1 (en) | 2013-05-14 | 2014-11-15 | Eco Recycling S R L | PROCESS FOR THE TREATMENT OF PHOTOVOLTAIC PANELS AT THE END OF LIFE |
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