EP4263887A1 - Procédé et installation de traitement de déchets contenant des composés métalliques - Google Patents
Procédé et installation de traitement de déchets contenant des composés métalliquesInfo
- Publication number
- EP4263887A1 EP4263887A1 EP21835336.5A EP21835336A EP4263887A1 EP 4263887 A1 EP4263887 A1 EP 4263887A1 EP 21835336 A EP21835336 A EP 21835336A EP 4263887 A1 EP4263887 A1 EP 4263887A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- waste
- ammonia
- leaching
- gaseous mixture
- aqueous solution
- 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
- 239000002699 waste material Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 62
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 24
- 238000012545 processing Methods 0.000 title claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 196
- 238000002386 leaching Methods 0.000 claims abstract description 122
- 239000007789 gas Substances 0.000 claims abstract description 111
- 239000000243 solution Substances 0.000 claims abstract description 105
- 239000007864 aqueous solution Substances 0.000 claims abstract description 93
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 79
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229920001021 polysulfide Polymers 0.000 claims abstract description 16
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 150000004763 sulfides Chemical class 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 95
- 239000000203 mixture Substances 0.000 claims description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 51
- 238000004519 manufacturing process Methods 0.000 claims description 45
- 238000000605 extraction Methods 0.000 claims description 37
- 239000005416 organic matter Substances 0.000 claims description 18
- 238000005063 solubilization Methods 0.000 claims description 15
- 230000007928 solubilization Effects 0.000 claims description 15
- 101000693367 Homo sapiens SUMO-activating enzyme subunit 1 Proteins 0.000 claims description 13
- 102100025809 SUMO-activating enzyme subunit 1 Human genes 0.000 claims description 13
- 238000009434 installation Methods 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 239000005077 polysulfide Substances 0.000 claims description 4
- 150000008117 polysulfides Polymers 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 108050008316 DNA endonuclease RBBP8 Proteins 0.000 description 13
- 102100035250 SUMO-activating enzyme subunit 2 Human genes 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 235000012501 ammonium carbonate Nutrition 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000013505 freshwater Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 241000195628 Chlorophyta Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000266272 Acidithiobacillus Species 0.000 description 1
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 241000736262 Microbiota Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000000735 allogeneic effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 208000010501 heavy metal poisoning Diseases 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000002211 methanization Effects 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
- C22B3/288—Quaternary ammonium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- TITLE Process and installation for the treatment of waste containing metal compounds
- the present invention relates to a process and an installation for treating waste containing metal compounds, in particular waste electrical and electronic equipment (D3E).
- waste electrical and electronic equipment D3E
- This waste is generally stored on storage and treatment sites, particularly in developing countries.
- the ecological impact of such storage is extremely heavy. Indeed, this storage leads to heavy metal pollution of the terrestrial, aquatic and atmospheric compartments, and the transport of waste to the storage sites has a significant energy cost.
- waste electrical and electronic equipment generally uses techniques used in the mining industry (eddy current separator, pyrometallurgy, hydrometallurgy, biometallurgy) but is technically complicated due to the complexity of the matrix to be processed compared to a conventional ore. Indeed, this waste is composed on average of 30% polymers (bakelite, epoxy, antioxidant, flame retardants), 30% ceramics and 40% metals, in particular copper, iron, aluminum, su zinc, tin, lead... .
- Eddy current separation is a technique using magnetic fields to separate ferrous and non-ferrous metals in dry conditions.
- it is not very selective in its current state for waste electrical and electronic equipment.
- To increase the selectivity it would be necessary to grind the waste extremely finely, which would increase the energy cost and would then make this technique potentially dangerous due to the possibility of the emergence of electric arcs.
- Biometallurgy which is itself extrapolated from mining techniques, is a promising approach that uses microorganisms in a liquid medium for the extraction of metals directly via an interaction between the microorganism and the metal or minerals of interest, or indirectly through a secondary metabolite synthesized by the microorganism (eg cyanide).
- bioleaching which is itself extrapolated from mining techniques, is a promising approach that uses microorganisms in a liquid medium for the extraction of metals directly via an interaction between the microorganism and the metal or minerals of interest, or indirectly through a secondary metabolite synthesized by the microorganism (eg cyanide).
- this technique is still under development and suffers from many shortcomings.
- this technique is still energy-intensive, due to the need to grind the waste to the state of electronic flour about 100 ⁇ m in diameter, and remains polluting, due to the use of acids or cyanide and the generation of dissolved heavy metals.
- the yield of this method is very low and is technically cumbersome to implement.
- the most successful method is an indirect bioleaching method which uses acidophilic bacteria.
- This technique is a dual process that uses ferro-oxidizing bacteria (eg Acidithiobacillus ferrooxydans) and sulfate-oxidizing bacteria (eg Acidithiobacillus thiooxidans)
- an object of the invention is to provide a waste treatment process and a device for implementing this process which has high selectivity, a yield compatible with industrial specifications, a limited risk of contamination and which minimizes chemical and energy inputs.
- the subject of the invention is a process for treating waste in the form of aggregates, in particular waste electrical and electronic equipment, said waste containing metal compounds, the method comprising the following steps:
- leaching of at least one metal compound from said waste comprising bringing said waste into contact with the leaching solution in an enclosure, to obtain, by reaction of the compound with the leaching solution, a leachate comprising a metal precipitated in the form of sulphides,
- the method according to the invention may also comprise one or more of the following characteristics, taken alone or in any technically possible combination:
- the supply of the gaseous mixture includes the production of said gaseous mixture by an anaerobic digester by decomposition of fermentable organic matter such as slurry;
- the waste is in the form of aggregates with a diameter of between 5 and 10 mm;
- an extraction phase from the gaseous mixture, of an intermediate gaseous mixture comprising hydrogen sulphide H2S, the extraction phase comprising bringing the gaseous mixture into contact with a first aqueous solution to solubilize at least one part of the ammonia of the gaseous mixture in the first aqueous solution, and an extraction, from the first aqueous solution, of the intermediate gaseous mixture depleted in ammonia, and,
- the extraction phase further comprises a withdrawal, from the aqueous solution, of a first aqueous solution enriched in ammonia, and the leaching step comprises bringing the aqueous solution enriched in ammonia into contact with the waste in said pregnant ;
- the leaching step comprises at least one oxidation-reduction reaction and at least one sulfur-reduction reaction between the metal compound and the leaching solution; • the method comprises sampling, from said enclosure, a mixture of residual gases comprising ammonia;
- the method comprises the production, from the mixture of residual gases, of a second aqueous solution enriched in ammonia, by dissolving at least part of the ammonia contained in the mixture of residual gases, the leaching step comprising bringing the second aqueous solution enriched in ammonia into contact with the waste in said enclosure;
- the gaseous mixture further comprises methane, the mixture of residual gases comprising methane, the method further comprising the production, from the mixture of residual gases, of electrical energy.
- the invention also relates to an installation for processing waste in the form of aggregates, in particular waste electrical and electronic equipment, said waste containing metal compounds, the installation comprising:
- a waste processing module comprising: i. a system for producing a leaching solution, configured to receive said gaseous mixture as an input, to bring said gaseous mixture into contact with an aqueous solution, and to produce at least one leaching solution comprising ammonia NH4OH and ammonium hydrosulphide (NH ⁇ sS and/or ammonium polysulphides, ii.
- a leaching system comprising an enclosure, the leaching system comprising means for bringing said waste into contact with the leaching solution in the enclosure to obtain, by reaction of at least one metal compound of said waste with the leaching solution, a leachate comprising a metal precipitated in the form of sulphides, and iii) means for extracting the leachate from the enclosure.
- Figure 1 is a diagram illustrating a treatment installation according to a first embodiment of the invention
- FIG 2 is a diagram illustrating part of a processing installation according to a second embodiment of the invention.
- the method according to the invention is a method for treating waste comprising metal compounds.
- Waste is for example waste equipment electrical and electronic.
- These metal compounds comprise for example at least one metal chosen from Cu, Fe, Al, Zn, Sn, Pb, Ni, Pt, Au, Ag and Pd, and/or at least one oxide of these metals.
- this waste comprises, for example, between 10% and 30% by mass of copper compounds, in particular Cu and/or CuO.
- the treatment installation 1 comprises a supply module 3 for a gas mixture, a waste treatment module 5 and an energy production module 7.
- the gas mixture supply module 3 is capable of supplying the waste treatment module 5 with a gas mixture MG comprising ammonia NH3 and hydrogen sulphide H2S.
- the gaseous mixture MG can also comprise methane CH 4 and/or carbon dioxide CO2.
- the gaseous mixture MG comprises between 50% and 70% methane, between 20% and 30% carbon dioxide, between 1% and 10% ammonia and between 1% and 30% sulphide of 'hydrogen.
- the presence of other contaminating gases, for example H 2 O, H 2 , other sulfur gases, organochlorines, organofluorines, siloxanes and dinitrogen... is also possible.
- the supply module 3 of the gas mixture comprises at least one anaerobic digester 9, configured to produce, by decomposition or fermentation of a fermentable organic matter such as slurry and / or algae, in particular green algae, a gaseous mixture MG comprising ammonia, hydrogen sulphide, methane and carbon dioxide.
- a fermentable organic matter such as slurry and / or algae, in particular green algae, a gaseous mixture MG comprising ammonia, hydrogen sulphide, methane and carbon dioxide.
- the anaerobic digester 9 comprises a tank 11 which can be hermetically sealed.
- the tank 11 has for example an internal volume of between 10 and 60 m 3 , in particular between 20 and 50 m 3 .
- the tank 11 is capable of being supplied with fermentable organic matter via a supply conduit 13.
- the tank 11 is provided with means for heating the organic matter received in the tank 11, adapted to maintain the interior of the tank 11 at a temperature for example between 50°C and 60°C.
- the tank 11 is designed to be able to operate with fermentable products loaded with salts or not.
- the tank 11 further comprises means for controlling and stabilizing the pH of the contents of the tank 11 in order to maintain the pH of the fermentable organic matter, during its fermentation, in particular between 7 and 8.
- the tank 11 comprises an outlet conduit 14 for the gaseous mixture MG produced by fermentation of the fermentable organic matter.
- the tank 11 further comprises a duct 15 for discharging the sludge produced by fermentation of the fermentable organic matter.
- the supply module 3 of the gas mixture further comprises a device 16 for controlling the flow rate of the gas mixture, in particular a gas holder.
- the flow control device 16 is arranged on the pipe 14 at the outlet of the tank 11, and is configured to control the flow of the gas mixture MG supplied to the waste treatment module 5.
- the waste treatment module 5 comprises a production system 17 of a leaching solution and a leaching system 19.
- the processing module 5 further comprises a recirculation system 21 .
- the production system 17 is configured to receive as input the gaseous mixture MG supplied by the supply module 3 of the gaseous mixture.
- the production system 17 is further configured to bring the gaseous mixture received MG into contact with an aqueous solution, and to produce at least one leaching solution denoted SL at the outlet, comprising ammonium hydrosulphide (NH ⁇ sS and/or or ammonium polysulphides and ammonia NH4OH
- the production system 17 is intended to supply the leaching solution SL to the leaching system 19.
- the production system 17 comprises at least one solubilization column, capable of receiving an aqueous solution (for example fresh water), of injecting the gaseous mixture into the aqueous solution in order to solubilize at least a part of the gases contained in the gas mixture, and to output the leaching solution.
- an aqueous solution for example fresh water
- the production system 17 comprises a first column 23 and a second column 25.
- the first column 23 is intended to extract, from the gaseous mixture MG, an intermediate gaseous mixture MGI comprising hydrogen sulphide, the concentration of hydrogen sulphide in the intermediate gaseous mixture MGI being greater than the concentration of hydrogen sulphide in the MG gas mixture.
- the first column 23 is preferably also intended to produce a first aqueous solution denoted SAE1 enriched in ammonia, by solubilization of the ammonia contained in the gaseous mixture MG. This first SAE1 aqueous solution enriched with ammonia constitutes an additional leaching solution.
- the first column 23 is configured to receive as input the gaseous mixture MG supplied by the supply module 3. To this end, the first column 23 is fluidly connected to the supply module 3 of the gas mixture, in particular to the conduit 14.
- the first column 23 comprises an internal volume capable of receiving a first aqueous solution (for example fresh water).
- the first column 23 comprises a feed conduit 27, capable of injecting the aqueous solution into the internal volume of the first column 23.
- the first column 23 is moreover configured to inject the gaseous mixture MG to solubilize, in the first aqueous solution, some of the gases contained in the gaseous mixture MG.
- the first column 23 comprises an injector 29, in particular a microbubble injector, fluidly connected to the supply module 3 of the gas mixture, in particular to the conduit 13.
- the injector 29 is intended to introduce the gas mixture MG into the first solution aqueous contained in column 23 in the form of microbubbles (for example with a diameter of between 20 and 200 ⁇ m).
- the injector 29 is placed in the lower part of the first column 23.
- the first column 23 preferably comprises a device for cooling the internal volume of the first column suitable for cooling and maintaining the first aqueous solution received at a temperature below room temperature (20° C.), for example at a temperature between 1°C and 5°C, especially 2°C.
- Maintaining this temperature makes it possible to promote the solubilization of the ammonia contained in the gaseous mixture MG, to produce ammonia, while limiting or avoiding the solubilization of hydrogen sulphide, and that of methane when the gaseous mixture further includes methane.
- solubility of ammonia in water is all the more important as the temperature is low, and much higher than that of hydrogen sulphide and methane.
- the gas mixture MG also comprises carbon dioxide, maintaining this temperature also makes it possible to promote the solubilization of the ammonia contained in the gas mixture MG in the form of ammonium carbonate (NH 4 ) 2 CO 3 .
- the first column 23 comprises an outlet 31 of the intermediate gas mixture MGI, intended to extract from the first column 23 the intermediate gas mixture MGI.
- the intermediate gas mixture MGI comprises hydrogen sulphide, the concentration of hydrogen sulphide in the intermediate gas mixture MGI being higher than the concentration of hydrogen sulphide in the gas mixture MG, due to the solubilization of ammonia in the first aqueous solution.
- the gaseous mixture MG also comprises methane
- the intermediate gaseous mixture MGI also comprises methane, which is not dissolved.
- the intermediate gaseous mixture MGI may also comprise ammonia not dissolved in the first aqueous solution.
- the first column 23 further comprises an outlet 33 of the first aqueous solution enriched in ammonia SAE1, and, if necessary, in ammonium carbonate. As described below, this outlet 33 is fluidically connected to the leaching system 19.
- the second column 25 is intended to produce, from the intermediate gaseous mixture MGI and, preferably, from a residual solution SR coming from the leaching system 19, the leaching solution SL comprising ammonia and hydrosulphide d ammonium and/or ammonium polysulfides.
- the second column 25 is configured to receive the intermediate gaseous mixture MGI supplied by the first column 23 as input. To this end, the second column 25 is fluidically connected to the first column 23, in particular to the outlet 31 .
- the second column 25 comprises an internal volume capable of receiving a second aqueous solution (for example fresh water).
- the second column 25 comprises a conduit 35 for supplying aqueous solution, capable of injecting the aqueous solution into the internal volume of the second column 25.
- the second column 25 also comprises a pipe 37 capable of injecting, into the internal volume of the second column, the residual solution SR supplied by the leaching system 19.
- This solution comprises, for example, ammonia and hydrosulphide of ammonium (NH 3 sS and/or ammonium polysulphides.
- the second column 25 is moreover configured to inject the intermediate gaseous mixture MGI supplied by the first column 23 to produce the leaching solution SL.
- the second column 25 comprises an injector 39, in particular a microbubble injector, fluidly connected to the first column 23, in particular to the outlet 31.
- the injector 39 is intended to introduce the intermediate gas mixture MGI into the second aqueous solution in the form of microbubbles.
- the injector 39 is placed in the lower part of the second column 25.
- the second column 25 preferably comprises a device for cooling the internal volume of the second column 25 capable of cooling and maintaining the aqueous solution received in the second column 25 at a temperature below the ambient temperature (20°C), for example at a temperature between 1°C and 5°C, in particular 2°C.
- the second column 25 comprises an outlet 41 for the leaching solution SL.
- the leaching system 19 is intended for the treatment of waste with the leaching solution SL.
- the leaching system 19 comprises an enclosure 45 fluidly connected to the production system 17.
- the leaching system 19 comprises means for bringing the waste into contact with the leaching solution in the enclosure 45 to obtain a leachate comprising particles of au least one metal contained in the waste, precipitated in the form of metal sulphides, and means for separating the leachate from the leaching solution SL and extracting the leachate from the enclosure 45.
- the enclosure 45 is for example a column, in particular cylindrical.
- the enclosure 45 comprises an internal volume 46 of leaching.
- the enclosure 45 comprises a device 47 for introducing waste into this internal volume 46, preferably fitted with a valve, so as to be able to control the flow of waste.
- the device 47 is for example placed at the top of the enclosure 45.
- the enclosure 45 includes a flange allowing air or oxygen to be routed in order to carry out potentially necessary oxidation operations or to vaporize the residual ammonia during maintenance.
- the enclosure 45 also includes means for bringing the leaching solution SL into contact with the waste in the internal volume 46.
- These contacting means comprise a device 49 for injecting the leaching solution SL into the internal volume 46.
- the injection device 49 is fluidically connected to the production system 17, in particular to the outlet 41 of the second column 25.
- the injection device 49 is for example placed in the upper part of the column.
- the injection device 49 comprises spraying means, for example nozzles, capable of spraying the leaching solution SL into the internal volume 46, in particular onto the waste contained in the enclosure 45.
- spraying means for example nozzles, capable of spraying the leaching solution SL into the internal volume 46, in particular onto the waste contained in the enclosure 45.
- the contacting means further comprise means for circulating the waste in the internal volume 46 of leaching.
- these circulating means comprise an ascending Archimedes screw 51, suitable for circulating the waste from the lower part of the enclosure 45 to its upper part.
- the enclosure 45 further comprises a device 50 for injecting the first aqueous solution SAE1 enriched with ammonia, constituting an additional leaching solution, into the internal volume 46.
- This injection device 50 for example disposed in part bass of enclosure 45 is fluidly connected to outlet 33 of first column 23.
- the enclosure 45 also preferably comprises a device 54 for injecting a second SAE2 aqueous solution enriched with ammonia, constituting a recycled leaching solution, into the internal volume 46.
- the enclosure 45 is preferably provided with an air inlet 57 generated by a compressor or a bone generator (for example a bone generator by the technique of adsorption by pressure inversion). Such an arrival makes it possible to inject air or oxygen, if the matrix to be extracted requires the presence of an oxidant at some point in the process.
- this air 57 or oxygen inlet facilitates maintenance to evacuate the ammonia residues in the recycling column 71 described below.
- This air inlet can also be used to convey an oxidizing solution, such as, for example, an ammonium persulphate solution.
- the leaching system 19 further comprises extraction means making it possible to separate the leachate (formed by reaction of the waste with the leaching solution) from the waste and the leaching solution, and to extract the leachate from the enclosure 45.
- These extraction means comprise for example at least one sieve 55, possibly mobile, the mesh of which is adapted to filter the waste leachate.
- the sieve 55 is adapted to let the leachate particles pass by blocking the waste granules.
- leachate generally comes in the form of particles with a diameter less than or equal to 0.3 mm, while waste is present in the form of granules with a diameter of between 5 and 10 mm.
- the sieve 55 may in this example have a mesh size of between 1 and 3 mm, in particular 2 mm.
- the sieve 55 is preferably arranged in the lower part of the enclosure 45, so as to receive the leachate particles produced by reaction of the waste with the leaching solution, falling in the lower part of the enclosure 45 under the effect of gravity. .
- the extraction means further comprise an extraction conduit 56 for the leachate filtered by the sieve 55 outside the enclosure 45.
- the extraction means further comprise a vertical grid 57, arranged in the enclosure 45 on the periphery of the internal volume 46 of leaching, and radially delimiting the internal volume 46.
- the grid 57 has a suitable mesh to filter the waste leachate, so as to extract the leachate from the internal volume 46.
- the extraction means further comprise means 59 for guiding the leachate extracted from the internal volume 46 by the grid 57 towards the sieve 55.
- These guiding means 59 comprise for example an inclined plate arranged in the enclosure 45 of so as to collect the leachate extracted from the internal volume 46 by the grid 57.
- the mesh of the grid 57 has a dimension greater than that of the mesh of the screen 55, so as to carry out a coarse filtering of the leachate before guiding the filtered leachate towards the screen 55.
- the grid 57 has a mesh between 2 and 4 mm, in particular 3 mm.
- the extraction means also include means for recovering residual waste from the enclosure 45.
- the residual waste corresponds to the waste from which the metals having reacted with the leaching solution have been extracted.
- these recovery means are arranged in the lower part of the internal leaching volume 46, and include a conduit 61 suitable for conveying the residual waste outside the enclosure 45.
- the recirculation system 21 is configured to extract from the leaching system 19, in particular from the enclosure 45, liquid or gaseous compounds resulting from the leaching reaction or which have not reacted, with a view to the reuse of at least some of these compounds.
- the recirculation system 21 is suitable for extracting from the enclosure 45 a residual solution SR comprising ammonia and/or ammonium hydrosulphide (NH ⁇ sS and/or ammonium polysulphides, in view of supplying this residual solution SR to the leaching solution SL production system 17.
- the recirculation system 21 thus makes it possible to reuse the ammonia and/or ammonium hydrosulphide and/or the ammonium polysulphides having no not reacted with the waste in enclosure 45.
- the recirculation system 21 comprises for example a conduit 65 provided with a pump 67, suitable for the extraction of the residual solution SR and its injection into the production system 17, in particular into the second column 25, via conduit 37.
- the conduit 65 is for example arranged in the lower part of the enclosure 45, in particular under the guide means 59 of the leachate.
- the recirculation system 21 is also suitable for extracting from the enclosure 45 a mixture of residual gases MGR, with a view to their reuse and/or recycling.
- residual gases include, for example, dihydrogen H 2 resulting from leaching reactions, as well as ammonia. If the gaseous mixture MG supplied by the supply module 3 comprises methane and/or carbon dioxide, the residual gases also comprise this or these gases.
- the recirculation system 21 comprises a gas extraction conduit 69.
- the conduit 69 is fluidly connected to the internal volume 46 of the enclosure, in particular is connected to the upper part of the enclosure 45, so as to collect and conveying the mixture of residual gases MGR outside the enclosure 45.
- the recirculation system 21 is also configured to produce, from the mixture of residual gases MGR, a second aqueous solution denoted SAE2 enriched in ammonia, by solubilization of the ammonia contained in the mixture of residual gases MGR.
- This second SAE2 aqueous solution is a recycled leaching solution.
- the recirculation system 21 comprises a recycling column 71 intended to produce the second aqueous solution SAE2.
- the recycling column 71 is configured to receive the mixture of residual gases MGR as input. To this end, the recycling column 71 is fluidically connected to the gas extraction conduit 69.
- the recycling column 71 comprises an internal volume capable of receiving an aqueous solution (for example fresh water). To this end, the recycling column 71 comprises a feed conduit 73, capable of injecting the aqueous solution into the internal volume of the recycling column 71 .
- an aqueous solution for example fresh water
- the recycling column 71 is moreover configured to inject the mixture of residual gases MGR to solubilize, in the aqueous solution, some of the gases contained in the mixture of residual gases MGR.
- the recycling column 71 comprises a gas diffuser 75, in particular a microbubble injector.
- the gas diffuser 75 is intended to introduce the mixture of residual gases MGR into the aqueous solution in the form of microbubbles.
- the gas diffuser 75 is placed in the lower part of the recycling column 71 .
- the recycling column 71 preferably comprises a device for cooling the internal volume of the recycling column, capable of cooling and maintaining the aqueous solution contained in this column at a temperature below ambient temperature (20° C.), for example at a temperature between 1°C and 5°C, in particular 2°C.
- Maintaining this temperature makes it possible to promote the solubilization of the ammonia contained in the mixture of residual gases MGR, to produce ammonia, while limiting or avoiding the solubilization of methane when the mixture of residual gases MGR comprises methane.
- the gaseous mixture MG also comprises carbon dioxide
- maintaining this temperature also makes it possible to promote the solubilization of the ammonia contained in the mixture of residual gases MGR in the form of ammonium carbonate.
- the recycling column 71 comprises a gas outlet 77, intended to extract from the recycling column 71 the gases not dissolved in the aqueous solution.
- gases include, for example, methane, carbon dioxide and/or dihydrogen.
- the recycling column 71 further comprises an outlet 79 for the second aqueous solution enriched in ammonia SAE2, and, where appropriate, in ammonium carbonate.
- This outlet 79 is fluidically connected to the leaching system 19, in particular to the enclosure 45, and makes it possible to inject the second aqueous solution enriched with SAE2 ammonia into the internal volume 46 of the enclosure.
- This outlet 79 comprises a three-way valve 81 allowing either to send the second aqueous solution enriched with ammonia SAE2 to the enclosure 45 or then to the outside to store it at the end of the process.
- ammonia that has not reacted in the enclosure 45 can be extracted therefrom and then reintroduced in the form of ammonia and ammonium carbonate.
- the energy production module 7 is configured to produce electrical energy from residual gases, in particular from gases not dissolved in the aqueous solution in the recycling column and extracted through outlet 77.
- the energy production module 7 is configured to produce electrical energy from the methane contained in the residual gases.
- the energy production module 7 is capable of producing electricity by combustion of methane.
- the energy production module 7 is intended for the power supply of the installation, in particular of the supply module 17 of the gaseous mixture and/or the leaching module 19.
- the method according to the invention comprises a step of supplying a gaseous mixture MG comprising ammonia and hydrogen sulphide, a step of production, from the gaseous mixture MG, by bringing the gaseous mixture into contact with a aqueous solution, of at least one leaching solution SL including ammonium polysulphides, a step for leaching at least one metal compound from the waste, comprising bringing said waste into contact with the leaching solution in an enclosure to obtain a leachate comprising solid particles of said metal precipitated in the form of sulphides, and a leachate extraction step outside the enclosure.
- the gas mixture MG comprises ammonia and hydrogen sulphide, and further comprises methane CH4 and/or carbon dioxide CO2.
- the step of supplying the gaseous mixture comprises for example the production of the gaseous mixture MG by, at least, an anaerobic digester by decomposition of a fermentable organic matter such as slurry and/or algae, in particular green algae, or even various agricultural or agri-food waste.
- a fermentable organic matter such as slurry and/or algae, in particular green algae, or even various agricultural or agri-food waste.
- the step of supplying the gaseous mixture MG comprises supplying the fermentable organic matter and decomposing the fermentable organic matter to produce the gaseous mixture MG.
- This decomposition is for example carried out in the presence of a microbiota consisting of allogeneic microorganisms coming directly from the fermentable input, and/or microorganisms specifically isolated upstream and inoculated during the decomposition process.
- the decomposition of the fermentable organic matter is preferably carried out at a temperature for example between 25°C and 60°C, at a pH between 7 and 8, and a low redox potential, between -300 mV and -500 mV, in particular about -400 mV.
- the step of supplying the gas mixture is for example implemented by the supply module 3 as described above.
- the step of supplying the gas mixture MG comprises supplying the tank 11 with fermentable organic matter via the supply line 13.
- the stage of decomposing the fermentable organic matter comprises heating the organic matter received in the tank 11 to a temperature for example between 50° C. and 60° C. taking advantage in part of the energy released by the microbial metabolism.
- the pH of the contents of the tank 11 is controlled to be maintained at 7 and 8.
- the step of supplying the gaseous mixture MG also comprises the evacuation of the gaseous mixture MG produced by fermentation of the fermentable organic matter via the conduit 13 of the outlet.
- the flow rate of the gas mixture supplied to the waste treatment module 5 is controlled by the device 16 for controlling the flow rate of the gas mixture.
- the sludge produced by fermentation of the fermentable organic matter is evacuated via the evacuation duct 15 to be subsequently recovered, for example, via a culture of Spirulina-type microalgae.
- the step for producing the leaching solution SL comprises bringing the gaseous mixture MG into contact with an aqueous solution, in particular fresh water, to produce ammonia NH4OH and ammonium hydrosulphide (NH ⁇ sS and / or ammonium polysulfides.
- This contacting is for example carried out by diffusing the gaseous mixture MG in at least one column of water.
- gaseous mixture MG also comprises carbon dioxide
- bringing the gaseous mixture MG into contact with the aqueous solution also produces ammonium carbonate (NH4) 2 CO 3 .
- solubility of ammonia in water is greater than that of hydrogen sulphide, which itself is greater than that of methane.
- the step of producing the leaching solution is carried out in at least two phases.
- the production step comprises in particular a phase of extraction, from the gaseous mixture MG, of an intermediate gaseous mixture MGI comprising hydrogen sulphide H2S, and a phase of production of the leaching solution SL by bringing the MGI intermediate gas mixture with a second aqueous solution.
- the phase of extraction of the intermediate gas mixture MGI comprises bringing the gas mixture MG into contact with a first aqueous solution to produce an aqueous solution enriched with the gas mixture, and the extraction, from the enriched aqueous solution, of the intermediate gas mixture MGI .
- the temperature of the first aqueous solution is below ambient temperature (20°C), for example between 1°C and 5°C, in particular 2°C.
- the gas mixture is thus depleted in ammonia.
- the intermediate gaseous mixture MGI, resulting from this depletion, is then extracted, with a view to producing the leaching solution SL.
- a first aqueous solution enriched with SAE1 ammonia produced by dissolving ammonia in the aqueous solution, is taken.
- This first aqueous solution enriched with SAE1 ammonia constitutes an additional leaching solution.
- the intermediate gaseous mixture MGI is brought into contact with a second aqueous solution.
- a residual SR solution comprising ammonia, in particular in the form of ammonia and ammonium hydrosulphide (NH ⁇ sS and/or ammonium polysulphides, is also injected into the second aqueous solution.
- the temperature of the second aqueous solution is below room temperature (20°C), for example between 1°C and 5°C, in particular 2°C.
- ammonia contained in the intermediate gas mixture MGI and/or in the residual solution SR is dissolved according to the following reactions:
- the leaching solution SL production step is implemented by the production system 17 as described above.
- the phase of extraction of the intermediate gas mixture MGI is for example implemented by means of the first column 23, and the phase of production of the leaching solution SL is implemented by means of the second column 25.
- the gaseous mixture MG is injected into the first column 23, containing the first aqueous solution, via the injector 29, preferably in the form of microbubbles.
- the intermediate gaseous mixture MGI is extracted from the first column 23 via outlet 31, while the first aqueous solution enriched in ammonia SAE1, and, if necessary, in ammonium carbonate is extracted via outlet 33.
- the intermediate gaseous mixture MGI is injected into the second column 25 containing the second aqueous solution, via the injector 39, preferably in the form of microbubbles.
- a residual SR solution supplied by the leaching system 19 is also injected into the second column 25.
- This residual SR solution comprises, for example, ammonia and ammonium hydrosulphide (NH ⁇ sS and/or ammonium polysulphides.
- the leaching solution SL is produced in the second column 25, and extracted from the second column 25 through the outlet 41.
- the leaching step includes bringing the waste into contact with the leaching solution in an enclosure to obtain a leachate comprising solid particles of said metal precipitated in the form of metal sulphides.
- the leaching solution SL is sprayed in the enclosure on the waste contained in the enclosure 45.
- the leaching solution including ammonia and ammonium hydrosulfide (and/or ammonium polysulfides), reacts with the metal compounds contained in the waste to produce a leachate.
- the leaching solution and the metal compounds generally react according to oxidation-reduction reactions, and sulfur-reduction reactions.
- the metal compounds comprise for example at least one metal chosen from Cu, Fe, Al, Zn, Sn, Pb, Ni, Pt, Au, Ag and Pd, and/or at least one oxide of these metals .
- the reaction of copper Cu and copper oxide CuO with the leaching solution is considered below.
- the copper compounds react with the ammonia according to the following possible reactions:
- This first reaction has the effect of consuming all the oxygen present in the enclosure.
- the reactions between the metal compounds and the leaching solution occur at least at atmospheric pressure.
- the reactions between the metal compounds and the leaching solution occur at a temperature between 30° C. and 50°.
- the enclosure 45 is hermetically sealed.
- the waste is circulated in the enclosure, so as to maximize the exposure of the waste to the leaching solution.
- the leaching step comprises injecting the first aqueous solution enriched with SAE1 ammonia produced during the extraction phase, constituting an additional leaching solution, into the internal volume 46, to bring the waste into contact with this first aqueous solution enriched with SAE1 ammonia.
- the injection of the first aqueous solution enriched with SAE1 ammonia is preferably carried out at the start of the leaching stage, so as to initiate the reactions by consuming the oxygen contained in the enclosure.
- the leaching step also includes an injection of additional ammonia into the enclosure, at the start of the leaching step, also so as to initiate the reactions. If the matrix to be extracted requires the presence of an oxidant at some point in the process, air, oxygen or an oxidizing solution, such as, for example, ammonium persulfate, is also injected into the enclosure 45, via arrival 57.
- the leaching step further comprises the injection of a second aqueous solution enriched with SAE2 ammonia, constituting a leaching solution recycled, in the enclosure.
- this recycled leaching solution is obtained by recycling residual gases extracted from enclosure 45.
- the leaching step is implemented by the leaching system 19 as described above, in particular in the enclosure 45.
- the waste is introduced into the internal leaching volume 46 via the introduction device 47.
- Bringing the leaching solution SL into contact with the waste in the internal volume 46 comprises the injection of the leaching solution SL into the internal volume 46 by the injection device 49, in particular by spraying via nozzles or any other suitable system. .
- the circulation of the waste in the internal volume 46 of leaching is carried out by means of the ascending Archimedes screw 51, by circulating the waste from the lower part of the enclosure 45 towards its part. high.
- the first aqueous solution enriched with ammonia SAE1 is injected by the injection device 50 into the internal volume 46.
- the second aqueous solution enriched with SAE2 ammonia, constituting a recycled leaching solution is injected into the internal volume 46 by the injection device 54.
- the leachate thus formed is extracted from enclosure 45.
- the leaching step being implemented by means of the leaching system 19, the extraction of the leachate from the internal volume 46 of the enclosure 45 is carried out through the grid 57, while the waste is retained by the grid 57 inside this internal volume 46.
- the leachate extracted is then guided by the guide means 59 towards the sieve 55.
- the leachate extracted is filtered by the sieve 55, collected in the lower part of the enclosure 45 and extracted via the extraction conduit 56 outside the enclosure 45.
- the method further comprises a step of recirculating compounds resulting from the leaching reaction or which have not reacted, in order to reuse at least some of these compounds.
- the recirculation step comprises in particular an extraction phase, outside the enclosure, of a residual solution SR comprising ammonia and/or ammonium hydrosulphide (NH ⁇ sS and/or polysulphides ammonium, with a view to reusing this residual solution SR for the production of the leaching solution SL.
- a residual solution SR comprising ammonia and/or ammonium hydrosulphide (NH ⁇ sS and/or polysulphides ammonium
- the extraction phase is implemented by the recirculation system 21 as described above.
- the residual solution SR is for example extracted by the pump 67 via the pipe 65 and injected into the production system 17, in particular into the second column 25, via the pipe 37.
- the recirculation step comprises the extraction of residual gases from the enclosure, and their reuse and/or recycling.
- residual gases include, for example, dihydrogen H 2 resulting from leaching reactions, as well as ammonia. If the gaseous mixture MG supplied during the supply step comprises methane and/or carbon dioxide, the residual gases also comprise this or these gases.
- the recirculation step includes the production, from the mixture of residual gases MGR, of a second aqueous solution enriched in ammonia SAE2, by solubilization of the ammonia contained in these residual gases.
- the extraction of the mixture of residual gases MGR from the enclosure, and, if necessary, the production of the second aqueous solution enriched in ammonia SAE2, are implemented by the recirculation system 21 .
- the mixture of residual gases MGR is extracted from the enclosure 45 by the gas extraction conduit 69 and conveyed by this conduit outside the enclosure 45.
- the residual gases are, if necessary, treated in the recycling column 71 to produce the second aqueous solution enriched in ammonia SAE2.
- the residual gas mixture MGR is introduced, via the gas extraction conduit 69, into the recycling column 71 previously filled with an aqueous solution.
- the mixture of residual gases MGR is injected, for example by the gas diffuser 75, in the form of microbubbles, to solubilize, in the aqueous solution, some of the gases.
- the aqueous solution is preferably maintained at a temperature below ambient temperature (20°C), for example between 1°C and 5°C, in particular 2°C.
- the other gases, such as methane, contained in the mixture of residual gases MGR are little or not dissolved.
- the residual gas mixture MGR is thus depleted in ammonia.
- the gases not solubilized in the aqueous solution, comprising for example methane, carbon dioxide and/or dihydrogen, are extracted from the recycling column through the gas outlet 77.
- the second aqueous solution enriched with SAE2 ammonia is taken via the outlet 79.
- this second aqueous solution is then injected into the internal volume 46 of the enclosure 45.
- the recirculation step comprises the production of electrical energy from the residual gases, in particular from methane
- This energy production is for example implemented by module 7 for energy production from residual gases, in particular from gases not solubilized in the aqueous solution in the recycling column and extracted through outlet 77.
- the electrical energy thus produced supplies the installation, in particular the supply module 17 of the gaseous mixture and/or the leaching module 19.
- this electrical energy is used to power other equipment.
- the leachate thus extracted comprising highly concentrated metal sulphides, can then be recovered, in particular by electroextraction.
- reaction is also applicable to the extraction of other metals such as silver, gold, palladium, nickel, platinum... as well as rare earths such as lanthanides and actinides.
- the process according to the invention has many advantages compared to traditional recycling processes.
- such a process consumes very few chemical inputs and energy, without releasing toxic vapours.
- the process can be implemented in a recycling center at the local level, which also limits the carbon impact due to road or sea transport of waste to major pyrometallurgical or hydrometallurgical centers.
- the process according to the invention is distinguished in particular by a higher yield, by the absence of biomass to be separated from the leachate - this is a dissociated bioleaching - at the end of the process. , by high selectivity and no risk of cross-contamination.
- the process according to the invention makes it possible to use a biomass input which is weakly methanizable or unsuitable for methanization (in particular a biomass rich in sulfur and/or in organic nitrogen).
- the energy balance of the process according to the invention is neutral or even negative, because it is possible to produce the energy necessary for the implementation of the process by the combustion of the residual methane.
- the gaseous mixture is not produced by an anaerobic digester, but by a desulfurization and deammonification unit, or even a hydrodesulfurization unit commonly used in the oil industry to remove sulfur from hydrocarbons.
- several treatment cycles can be considered in order to perfectly extract the metals of interest. These cycles can be implemented in the same installation, in particular in the same leaching device, or by combining several leaching devices.
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Abstract
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FR2013829A FR3118062B1 (fr) | 2020-12-21 | 2020-12-21 | Procédé et installation de traitement de déchets contenant des composés métalliques |
PCT/EP2021/086880 WO2022136316A1 (fr) | 2020-12-21 | 2021-12-20 | Procédé et installation de traitement de déchets contenant des composés métalliques |
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US3971652A (en) * | 1972-02-21 | 1976-07-27 | Metallurgical Development Company | Ammoniacal extraction of copper from metallic materials |
JPH0698356B2 (ja) * | 1990-01-25 | 1994-12-07 | 荏原インフイルコ株式会社 | 有機性汚水の処理方法 |
US5173276A (en) * | 1990-05-30 | 1992-12-22 | Cato Research Corporation | Method for recovery of copper from copper-containing materials |
US7153427B2 (en) * | 2002-07-22 | 2006-12-26 | Environmental Energy & Engineering Co. | Nitrogen recovery system and method using heated air as stripping gas |
NL2018962B1 (en) * | 2017-05-22 | 2018-12-04 | Elemetal Holding B V | Process for metal recovery by ammonia leaching and solvent extraction with gas desorption and absorption |
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