US 12,662,390 B2
Method and system for supercritical fluid extraction of metal
Gisele Azimi, Toronto (CA); Yuxiang Bill Yao, Calgary (CA); Jiakai Zhang, Toronto (CA); and John Joseph Naguib Anawati, Ottawa (CA)
Assigned to THE GOVERNING COUNCIL OF THE UNIVERSITY OF TORONTO
Appl. No. 17/045,128
Filed by The Governing Council of the University of Toronto, Toronto (CA)
PCT Filed Nov. 22, 2018, PCT No. PCT/IB2018/059196
§ 371(c)(1), (2) Date Oct. 2, 2020,
PCT Pub. No. WO2019/193413, PCT Pub. Date Oct. 10, 2019.
Claims priority of provisional application 62/651,848, filed on Apr. 3, 2018.
Prior Publication US 2021/0265678 A1, Aug. 26, 2021
Int. Cl. H01M 10/54 (2006.01); B01J 3/00 (2006.01); C01F 17/224 (2020.01); C01F 17/276 (2020.01); C22B 3/00 (2006.01); C22B 7/00 (2006.01); C22B 11/00 (2006.01); C22B 26/12 (2006.01); C22B 30/02 (2006.01); C22B 59/00 (2006.01); B01D 11/02 (2006.01)
CPC C01F 17/276 (2020.01) [B01J 3/008 (2013.01); C01F 17/224 (2020.01); C22B 7/007 (2013.01); C22B 11/046 (2013.01); C22B 23/0438 (2013.01); C22B 26/12 (2013.01); C22B 30/02 (2013.01); C22B 59/00 (2013.01); H01M 10/54 (2013.01); B01D 11/0203 (2013.01); B01J 3/002 (2013.01)] 20 Claims
 
1. A method for supercritical fluid extraction of at least one target metal from a source, the method comprising:
providing a reactor chamber;
providing a source selected from the group consisting of a battery, a permanent magnet, a bauxite residue, and an activated carbon, the source comprising:
the at least one target metal, being chemically bonded to at least one additional metal via metallic bonds; and
at least one impurity;
pre-processing the source;
providing a chelating agent being one or more compounds selected from the group consisting of an organophosphorus compound, a ketone, a dithiocarbamate, a crown ether, a fluorinated compound, 8-hydroxyquinoline, 7-(1-vinyl-3,3,5,5-tetramethylhexyl)-8-hydroxyquinoline, an amide, an organic acid, a quaternary ammonium salt, and an oxime;
providing a solvent;
providing a co-solvent;
adding the pre-processed source the chelating agent, the solvent and the co-solvent into the reactor chamber;
adjusting the temperature in the reactor chamber to a range of about 35 to about 55° C. and the pressure in the reactor chamber so that the solvent is heated and compressed above its critical temperature and pressure;
optionally, providing mechanical agitation to the reactor chamber; and
recovering a chelate comprising the target metal,
wherein:
the organophosphorus compound is selected from the group consisting of tributyl phosphate (TBP), tributyl phosphate-nitric acid (TBP-HNO3), trialkylphosphine oxide-nitric acid (TRPO-HNO3), tributylphosphine oxide (TBPO), trioctylphosphine oxide (TOPO), triphenylphosphine oxide (TPPO), bis(2-ethylhexyl) phosphate (DEHPA), bis(2-ethylhexyl)monothiophosphoric acid (D2EHTPA), dialkyl phosphinic acid (Cyanex 272), bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301, Cyanex 302), bis-(2-ethylhexyl)phosphoric acid (B2EHPA), carbamoylmethylene phosphine oxide (CMPO), 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A), phosphonoacetic acid (PAA) and N,N-bisphosphono(methyl)glycine (BPG);
the ketone is selected from the group consisting of acetylacetone (AA), trifluoroacetylacetone (TFA), hexafluoroacetylacetone (HFA), trifluoroacetylacetone (TAA), thenoyltrifluoroacetone (TTA), methyl isobutyl ketone (MIBK), 2,2,7-trimethyl-3,5-octanedione (TOD), 2,2,6,6-tetramethyl-3,5-heptanedione (THD), 1,1-dimethyl-3,5-hexanedione (DMHD), 2,6-dimethyl-3,5-heptanedione (DIBM), 1,1,1-trifluoro-4-phenyl-2,5-butanedione (TFBZM) and 1-phenyl-1,3-pentanedione (BZAC);
the dithiocarbamate is selected from the group consisting of lithium bis(trifluoroethyl)dithiocarbamate (LiFDDC), diethyldithiocarbamate (DDC), bis(trifluoroethyl)dithiocarbamate (FDDC), dipropyldithiocarbamate (P3DC), dibutyldithiocarbamate (BDC), dipentyldithiocarbamate (P5DC), dihexyldithiocarbamate (HDC), pyrrolidinedithiocarbamate (PDC) and tetrabutylammonium dibutyldithiocarbamate TBA (BDC);
the crown ether is selected from the group consisting of 2,2-dicyclohexyl-1,4,7,10,13,16,19-heptaoxacyclohenicosane (DCH21C7), 2,3,11,12-dicyclohexano-1,4,7,10,13,16-hexaoxacyclooctadecane (DCH18C6), 1,4,7,10,13-pentaoxacyclopentadecane (15C5), bistriazolo-crown ether I (Crown I), bistriazolo-crown ether II (Crown II) and bistriazolo-crown ether III (Crown III);
the fluorinated compound is selected from the group consisting of 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-oactanedione (HFOD), 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (HFAC), thenoyltrifluoroacetone (TTFA), pentadecafluorooactanoic acid (HPFOA), ammonium perfluoropolyether piperazindithiocarbamate (FE-APDC), perfluoropolyether picolylamine (FE-PA), ammonium perfluoropolyether dithiocarbamate (FE-DC), perfluoropolyether dithiol (FE-DT) and heptafluorobutanoylpivaroylmethane (FOD);
the organic acid is selected from the group consisting of neodecanoic acid, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepentaacetic dianhydride (DTPA-DA) and triethylenetetraaminehexaacetic acid (H6TTHA);
the amide is selected from the group consisting of N,N,N′,N′-tetraoctyldiglycolamide (TODGA), N,N,N′,N′-tetraisobutyl-3-oxapentanediamide (TiBODA), N,N,N′,N′-tetrabutyl-3-oxapentanediamide (TBODA) and N,N′-dimethyl-N,N′-dibutyltetradecylmalonamide (DMDBTDMADBBP);
the quaternary ammonium salt is N-methyl-N,N,N-trioctylammonium chloride; and
the oxime is 2-hydroxy-5-nonylbenzophenone oxime.