Palladium Recovery from Wastes From Fundamental Studies to Applications

Size: px

Start display at page:

Download "Palladium Recovery from Wastes From Fundamental Studies to Applications"

Elaine Richards
5 years ago
Views:

Meyer Laboratoire des Systèmes Hybrides pour la Séparation (LHYS)

CNRS/CEA/ENSCM/UM2 damien.bourgeois@cea.

1 Palladium Recovery from Wastes From Fundamental Studies to Applications Damien Bourgeois, Rémi Poirot, Régis Mastretta, Valentin Lacanau, Daniel Meyer Laboratoire des Systèmes Hybrides pour la Séparation (LHYS) Marcoule Institute for Separative Chemistry (ICSM) - FRANCE UMR5257 CNRS/CEA/ENSCM/UM2 damien.bourgeois@cea.fr * Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

complex flows Recycling of metals Clean nuclear energy United Nations Environment Program, 2009 Need for understanding the driving force

2 Context Solvent Extraction One of the base techniques in hydrometallurgy Extraction of one metal from aqueous to organic phase Solvent: extractant in organic phase Separation from other metal(s) left in aqueous layer Metals: M1 and M2 in aqueous phase Challenges: deal with complex flows Recycling of metals Clean nuclear energy United Nations Environment Program, 2009 Need for understanding the driving force of metals separation Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

The extractant: a metal complexing agent From a coordination chemistry point of view: Driving force: coordination of the cation in the organic phase Example: U(VI) extraction with phosphorus reagents

3 The extractant: a metal complexing agent From a coordination chemistry point of view: Driving force: coordination of the cation in the organic phase Example: U(VI) extraction with phosphorus reagents => P(O)(OR) 3 < P(O)R(OR) 2 < P(O)R 3 Or also Pd(II) extraction with sulfides (Pearson - HSAB) Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

The extractant: a metal complexing agent Integration of modern coordination chemistry concepts See eg. work by P. Tasker et al. on Cu(II) extraction with pyrrazoles-phenates => buttressing effect P.

4 The extractant: a metal complexing agent Integration of modern coordination chemistry concepts See eg. work by P. Tasker et al. on Cu(II) extraction with pyrrazoles-phenates => buttressing effect P. Tasker et al., Pacifichem, 2015 Also involved into Ni(II) extraction with a synergistic mixture of α-hydroxyoximes and carboxylic acids Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

Meridiano, PhD thesis, Université d Orsay, 2009, B. Gannaz, PhD thesis, Université d Orsay, 2007 C. R.

5 The solvent: an extracting medium From a physical chemistry point of view: Monomers CAC progressive aggregation [extractant] Aqueous phase Formation of reverse micelles in the organic phase Extractant = amphiphile Y. Meridiano, PhD thesis, Université d Orsay, 2009, B. Gannaz, PhD thesis, Université d Orsay, 2007 C. R. Chimie 10 (2007) Extractants in the nuclear fuel cycle Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

6 Malonamides: good Pd chelating agents Extraction mechanism & third solid phase Precipitate at interface Increase in [Pd] org heptane water Insoluble in heptane O 3 N NO 3 Pd C 7 H 15 N N C 7 H 15 CH 3 O O CH 3 O C 5 H 11 Formation of stable Pd(II) complexes Poirot, R., Solvent Extraction and Ion exchange, 2014, 32, Amide moiety vs Soft ligand (S, N) Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

7 Comparison between Pd 2+ and Nd 3+ Pd(II) & Nd(III): relationships between D and I 0 SAXS intensity at q = 0 Heptane: Toluene: 10 D(Pd) D(Nd) I0 I D(Pd) D(Nd) I0 0 2 D 9 1,8 D 9 1,8 8 1,6 8 1,6 7 1,4 7 1, ,2 1 0,8 I 0 (cm -1 ) ,2 1 0,8 I 0 (cm -1 ) 3 0,6 3 0,6 2 0,4 2 0,4 1 0,2 1 0, [HNO 3 ] aq,éq (mol/l) [HNO 3 ] aq,éq (mol/l) [DMDOHEMA] = 0,3 M Nd(III) extraction occurs only in the presence of aggregation Note: - All other parameters (eg. speciation in aq. phase) are eliminated Poirot, R. et al., ChemPhysChem, 2016, Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

Comparison between H- and F-malonamides Flexible zig-zag chain vs

, ChemPhysChem 2017, 18, 3583-3594 H-Malonamide in CH 2 Cl 2

10% 0% Nd Nd Pd Pd 0% Nd Nd Pd Pd B Braibant et al., J. Fluorine Chem.

8 Comparison between H- and F-malonamides Flexible zig-zag chain vs Rigid helicoidal chain H-Malonamides F-Malonamides B Braibant et al., ChemPhysChem 2017, 18, H-Malonamide in CH 2 Cl 2 F-Malonamide in CH 2 Cl 2 Nd Extraction yield Extraction yield 60% 50% Pd, Nd S Pd,Nd = 1.9 S Pd,Nd = 34 60% 50% 40% 40% 30% 30% 20% 20% Pd only Pd only Nd 10% 10% 0% Nd Nd Pd Pd 0% Nd Nd Pd Pd B Braibant et al., J. Fluorine Chem. 2017, 200, Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

9 Aggregation as a trigger for Pd/Nd selectivity Good understanding of the driving forces of solvent extraction: Low aggregation vs High aggregation Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

10 Consequences for selective Pd extraction Aggregation can be induced by two different triggers: DPd Role of diluent: 100/0 80/20 50/50 20/80 0/100 Ratio Heptane/Toluène Aq. Phase: [HNO 3 ] = 1M, [LiNO 3 ] = 2M Org. Phase: DMDBTDMA 0,5M in diluent SPd/Nd DPd SPd/Nd DNd 0,20 0,18 0,16 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0,00 DNd SPd/Nd Role of [HNO 3 ] aq 1,2 1,5 1,8 2,1 2,3 [HNO 3 ] (mol/l) Org. Phase: DMDBTDMA 0,6M in toluene (DPd = 8 to 10) SPd/Nd Optimum Pd extraction with 1-3M [HNO 3 ] aqueous phase & aromatic diluent Well-chosen formulation of solvent in order to perform desired separation Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

11 Application to Pd recovery from WEEE? WEEE as a new source for numerous metals United Nations Environment Program, 2009 Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

12 Application to Pd recovery from WEEE? 12 Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

10-20% recycled with pyrochemical process (see eg.

13 Application to Pd recovery from WEEE? WEEE as a new source for numerous metals United Nations Environment Program, 2009 No systematic reprocessing in Europe: 10-20% recycled with pyrochemical process (see eg. UMICORE) Adaptation of Cu-smelters in operation Price of WEEE depends on Cu and Au contents Need for supplementary SX solutions Pd value in waste neglected so far Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

1) Fit into existing process Ex: Recycling of REEs at La Rochelle plant (Solvay) -> * low CAPEX * materials selection 2) Design new selective

14 Solvent Extraction in Recycling Shredding 1) Acid leaching 2) Solvent Extraction 3) Conversion Wastes Variability Complexity Which system? Which process? 1) Fit into existing process Ex: Recycling of REEs at La Rochelle plant (Solvay) -> * low CAPEX * materials selection 2) Design new selective extractant Only limit: imagination of chemists! and REACH! 3) Divert already developped technology Benefit from previous R&D studies, but need to adapt & know well SX systems Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

15 Where is Pd in WEEE? Pd employed in a Ag/Pd alloys in MLCC SEM images Do not use HCl for Pd leaching! Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

Then complete dissolution in diluted NHO 3 during 2h at 60 C Concentration in solution (mg/l) Ag Al Ba Cu Fe Nd Ni Pb Pd Sn Ti Y Zn 10-900 <LoQ <15

16 Smart Pd leaching Strategy Avoid grinding & aqua regia Selective dissolution of solders All components fall! After 5min K. Yoo, Materials Transactions, 2012, 53, X. Zhang, ACS Sustainable Chem. Eng., 2015, 3, but Cu (>95%) and Au remain on the PCB! Then complete dissolution in diluted NHO 3 during 2h at 60 C Concentration in solution (mg/l) Ag Al Ba Cu Fe Nd Ni Pb Pd Sn Ti Y Zn <LoQ < <LoQ <20 <10 <30 <40 Rather simple Pd solution Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

17 What about other metals contained in WEEE? Selective extration of Pd from mixture of metals: (in heptane) Patented (07/2014) WO A1 REEs Major issue = Fe other base metals (Co, Ni, Zn, Al ) = OK Similar behavior of Fe(III) and Nd(III) Fe Extraction of other base metals found in leach liquor Metal D(M) Extraction % Amount in organic phase (mg/l) Pb 0, ,7 Cu 0, ,9 Al < 0,05 5 <LQ Zn 0,02 2 2,3 Ni 0,04 4 1,0 Sn Also check Cu Evaluated as Sn(II) chloride Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

18 Malonamide-based solvent for selective Pd extraction Choice of malonamide: Extraction of Fe(III) with DMDBTDMA in toluene: D S Pd/Fe = Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

19 Fe-scrubbing & Pd-stripping strategy Principle: use only water! Pilot metals presence in solvent via aqueous HNO 3 concentration After extraction organic phase is loaded with HNO 3 Contact with water => apparent equilibrium [HNO 3 ] aq ~ 1-1,5M => Scrub Fe Contact with water => apparent equilibrium [HNO 3 ] aq ~ 0,2M => Strip Pd And optimize O/A ratio Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

20 Pd recovery at the lab (X-current) 10 ml scale Glass vials Magnetic stirring AQUEOUS FEED EXTRACTION Extraction % Aq phase content Pd 98 mg/l Fe 972 mg/l Cu 1942 mg/l Org phase content DMDBTDMA 0,6M in toluene Pd 99% Pd 102 mg/l Fe 19% Fe 184 mg/l A/O=2 ; N=2 ; 10min Cu 1,4% Cu 27 mg/l Other metals discarded for clarity SCRUBBING Loss/Elimination % Org phase content H 2 O Pd 1% Pd 101 mg/l Fe 89% Fe 20 mg/l O/A=10 ; N=1 ; 60min Cu 93% Cu 1,7 mg/l SCRUBBING Loss/Elimination % Org phase content HNO 3 1M Pd 1% Pd 100 mg/l Fe 98% Fe 3,2 mg/l O/A=10 ; N=1 ; 60min Cu >99% Cu < LoQ Pd STRIPPING Recovery % Aq phase content NaCl 0,5M Pd 85% Pd 854 mg/l Purity % Fe 5 mg/l O/A=10 ; N=1 ; 60min Pd 99,5% Cu < LoQ Keep some Pd in solvent! NEW EXTRACTION CYCLE WITH SOLVENT Org phase content Same initial aq feed Pd 116 mg/l Fe 188 mg/l A/O=2 ; N=2 ; 10min Cu 23 mg/l Target: Pd(II) chloride solution ca 1 g/l Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

21 Conclusions & Perspectives Nice system for Pd: easy extraction, easy stripping lab scale Control of the whole process via [HNO 3 ] only! Leave Cu & Au -> solid residue still valuable Perspectives towards further development: Treat aqueous flows -> already other metals separated! (Sn, Pb, Fe) Develop on larger scale with counter-current process (already modelled) Benchmark with other solvents (including stripping!) And. ready to discuss about industrial relevant processes! Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

Marcoule Institute for Separative Chemistry (UMR

22 Acknowledgments Rémi Poirot Daniel Meyer Régis Mastretta And thank you for your attention! Marcoule Institute for Separative Chemistry (UMR 5257 ICSM) PROMETIA Scientific Seminar, Berlin, dec 14 th, /22

Characterization of lanthanide and actinide complexes in the DIAMEX- SANEX process

Characterization of lanthanide and actinide complexes in the DIAMEX- SANEX process Julie MULLER 1 Laurence BERTHON 1, Nicole ZORZ 1, Jean-Pierre SIMONIN 2 1 CEA, DEN, DRCP, SCPS, LILA, F-30207 Bagnols-sur-Cèze,