Purolite Ion Exchange Resins for Recovery and Purification of Rhenium

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1 Introduction to Purolite Founded in 1982 by Stefan and Don Brodie Globally diversified business: Purolite Ion Exchange Resins for Recovery and Purification of Rhenium 7th International Symposium on Technetium and Rhenium Science and Utilization Moscow, Russia July 4 8, 2011 Compiled by Mikhail Mikhaylenko, Hydrometallurgy Manager PUROLITE INTERNATIONAL LIMITED Sales offices in 42 countries, distributors selling in an additional 16 countries Manufacturing in USA, Romania, China Five R&D facilities in different countries including Russia Purolite is the only pure-play IER manufacturer Purolite is 2 nd 3 rd Largest Ion Exchange Resin Company in Industry ISTR-2011 Moscow M. Mikhaylenko, Purolite 2

2 Rhenium Selective Resins Purolite I. Recovery Of Rhenium in Absence of Molybdenum ISTR-2011 Moscow M. Mikhaylenko, Purolite 3 ISTR-2011 Moscow M. Mikhaylenko, Purolite 4

3 Summarized Process Arrangement Isotherms Ammonia aqua Return to sorption Industrial Re containing stream Filtration Sorption Desorption IXR Ammonium perrhenate Conversion to salt form Rhenium sorption from rinsing sulfuric acid on (1) A170/4675 (2) contender WBA resin Sulfuric acid strength is 300 g/l (a) and 600 g/l (b) Blokhin, A. et al. ISTR-2011 Moscow M. Mikhaylenko, Purolite 5 ISTR-2011 Moscow M. Mikhaylenko, Purolite 6 Rhenium fixation on resin, g/l Rhenium fixation on resin, g/l Equilibrium Re concentration, mg/l b Equilibrium Re concentration, mg/l а

4 Kinetic study for Purolite A172/4635 II. Recovery Of Rhenium From Industrial Streams Bearing Molybdenum Composition of the artificial solution, mg/l: Mo 3200; Re 12.5; P 70.0; Cl 16.0; SO g/l; ph = 1.2 Volkov, V. et al. Metal uptake by the resin, g/l Mo Re Sorption elapsed time, hours ISTR-2011 Moscow M. Mikhaylenko, Purolite 7 ISTR-2011 Moscow M. Mikhaylenko, Purolite 8

5 Purolite A172/4635: column test Purolite A172/4635: Desorption study Solution matrix, mg/l: Re 18.9; Mo 3426; ph = Flow rate 10 BV/hour Volkov, V. et al. Re conc.in outlet normalized to inlet conc., % Legend: Re Mo Elapsed time, hours Desorption by 5% ammonia Residual capacity in the resin, g/l Concentration in entire desorbate, mg/l Time desorption, hours Mo Re Separation number, (Re/Mo) d /(Re/Mo) feed Volkov, V. et al. ISTR-2011 Moscow M. Mikhaylenko, Purolite 9 ISTR-2011 Moscow M. Mikhaylenko, Purolite 10

6 Removal of Mo from Re by Purolite S957 Resin Artificial feed solution, mg/l Re Mo Fe +3 Cu H 2 SO g/l III. Recovery Of Rhenium From Different Acids Resin capacity, g/l: Re Mo Fe +3 Cu Mo ( ) Separation Number (resin to feed): Re Volkov, V. et al. ( ) =1464. ISTR-2011 Moscow M. Mikhaylenko, Purolite 11 ISTR-2011 Moscow M. Mikhaylenko, Purolite 12

7 g/ln,esinrnotioixapurolef120ritre()a-170/g1pmh mix: Rhenium Sorption Isotherm 4635NaCl3HCl 3,5 l3,0 2,5 2,0 1,5 A170 A600 3,5 3,0 2,5 2,0 1,5 Chloride Matrix: Re Distribution Parameter A ,0 0,1 0,2 0,3 0,4 0,5 0,6 EquilibriumReconcentration,g/lDConcentration of HCl, mol/l 1, ga600la-600: SBA resin, Type I, gel DPurolite 1, Conc. of NH 4 Cl in 0.1M HCl, mol/l Blokhin, A. et al. ISTR-2011 Moscow M. Mikhaylenko, Purolite 13 Blokhin, A. et al. ISTR-2011 Moscow M. Mikhaylenko, Purolite 14

8 Nitrate Matrix: Re Distribution Parameter 2,5 2,0 gda600l2,0 DPurolite 2,5 A170 A170 0,0 0,5 1,0 1,5 2,0 2,5 3,0 A-600: SBA resin, Type I, gel ga600l1,5 1,5 IV. Recovery of Rhenium from Uranium Barren Solutions at ISL Operations 1,0 1,0 0,5 0,0 0,5 1,0 1,5 2,0 2,5 3,0 Concentration of HNO 3, mol/l 0,5 Conc. of NH 4 NO 3 in 0.1M HNO 3, mol/l Blokhin, A. et al. ISTR-2011 Moscow M. Mikhaylenko, Purolite 15 ISTR-2011 Moscow M. Mikhaylenko, Purolite 16

9 Rhenium Recovery in the ISL Processes Current Users of A170 Resin H 2 SO 4 + NH 4 NO 3 Present Scheme H 2 SO 4 ; ph l U ~ 100 ppm Re ~ ppm Pregnant resin U stripping Uranium concentrate SBA Sulfuric acid IN-SITU LEACHING New Implementation Re ~ ppm U ~ 5 ppm H2SO4 A170 NH 4 OH Re stripping NH 4 ReO 4 (Re ~500 ppm) Rhenium recovery from produced sulfuric acid at copper smelters: KGHM Ecoren, Poland Kennecott Utah Copper (Rio Tinto), USA Rhenium recovery from uranium barren solutions: Navoi GMK, Uzbekistan Processing of spent Re-Pt catalysts: Several enterprises in Russia Several new projects under development in USA, Russia and Asia. ISTR-2011 Moscow M. Mikhaylenko, Purolite 17 ISTR-2011 Moscow M. Mikhaylenko, Purolite 18

10 ACKNOWLEDGEMENTS to to Prof. Alexander A. Blokhin (Technical University, Saint- Petersburg), his fellow-workers and students, Vladimir P. Volkov (ZAO NPO GPS, Moscow) and his fellowworkers for their valuable inputs in elaboration of presented data. ISTR-2011 Moscow M. Mikhaylenko, Purolite 19