ACTIVITATI

Cod proiect

COFUND-ERANET-ERAMIN-SUPERMET
Contract nr: 48 / 2018

Title

Recovery of Precious Metals from Spent Catalysts by Supercritical CO2 Extraction Assisted by Polymers

Acronym

SUPERMET

Domain

4 – Eco-nano-technologies and advanced materials

Contracting authority

Executive Unit for Financing Higher Education, Research, Development and Innovation (UEFISCDI)

Abstract

SUPERMET project proposes to explore an eco-friendly disruptive technology for the recycling of precious metals, especially palladium (Pd) and platinum (Pt), from spent catalysts, e.g. from petrochemistry catalysts, by extraction in supercritical CO2 (scCO2) thanks to complexing polymers bringing the insoluble precious metals into the scCO2 medium. Precious metals are used extensively in applications for catalysis not only in the petrochemistry, but also in the field of automotive (three way catalyst) and in the synthesis of fine chemicals. The scarcity of these metals poses a risk for the European countries which do not have this primary resource.

The pyrometallurgical and hydrometallurgical state of the art techniques developed for the recovery of these metals are energy-intensive, destructive, and generate large volumes of toxic effluents. With our proposed innovative recycling process, the catalytic support and the precious metal remain intact and can be reused as well as the used CO2 and polymer, so that there are no toxic effluents. Due to adjustable solvent properties of scCO2, the dissolved polymer-metal complex can be removed from the CO2 simply by depressurization. So, this new process is eco-efficient and solves a core problem of the state of the art processes.

The SUPERMET project, coordinated by the Charles Gerhardt Institute of Montpellier (ICGM, France), brings together partners from Germany, Romania and France: the Fraunhofer Institute for Chemical Technology (Fraunhofer ICT, Germany), Heraeus Deutschland GmbH & Co KG (Heraeus, Germany), the National Institute for Research and Development in Optoelectronics (INOE, ICIA Cluj-Napoca subsidiary, Romania) and the Supercritical Fluids Innovation Association (IFS, France).

Partners

• Project Coordinator: Institute Charles Gerhardt of Montpellier (ICGM), France
  Dr Patrick Lacroix-Desmazes
• Fraunhofer Institute for Chemical Technology (ICT), Germany
• HERAEUS, Germany
• Supercritical Fluid Innovation (IFS), France

Project objective

The SUPERMET objective is to develop an eco-friendly extraction method to recover precious metals (e.g. Pd, Pt) from spent catalysts using supercritical CO2 (scCO2) and complexing polymers as extractants, generating a minimum of secondary effluents.

Estimated results

• Report on testing of virgin catalysts
• Report on testing of spent catalyst
• Report on the pre-treatment of catalysts for the extraction of precious metals
• Report on ability of synthesized polymers to complex metals
• Report on the post-treatment of extracted products (precious metals)
• Product characterization report (for obtained precious metals)
• Participation / organization of meetings within the project, workshop
• Results disseminated through publication of ISI articles and participation in international conferences

Obtained results

Press release, June 2109

Press release 14.06.2018

Press release, December 2018

Published paper: Lucrare publicată: M. Senila, O. Cadar, T. Janisch, P. Lacroix-Desmazes, “Method Validation for Determining Platinum and Palladium in Catalysts using Inductively Coupled Plasma Optical Emission Spectrometry”, International Conference on Analytical Chemistry and Applied Spectroscopy (ICACAS 2019), June 20-21 2019, Venice (Italy)

Obtained results Stage 1 – 2018

• Report (stage 1)
• Participation at Kick-off meeting (Montpellier, France, May 23, 2018)
• Participation at project meeting (Hanau, Germany, Octomber 17-18, 2018)
• Visit of project coordinator at ICIA (Cluj-Napoca, Romania, July 23-25, 2018)
• Organization of video meeting (September 4, 2018)

Obtained results Stage 2 – 2019

• Report (stage 2)
• Participation at project meeting (Cluj-Napoca, Romania, May 21-22, 2019)
• Participation at project meeting (Pfintzal, Germany, Octomber 14, 2019)
• Participation at videomeetings (January 10, 2019; August 30, 2019)

Obtained results Stage 3 2020

• Participation at videomeetings (January 14, 2020; May 12, 2020)
• Published ISI paper: Andrea Ruiu, Bernhard Bauer-Siebenlist, Marin Senila, Thorsten Janisch, Dominique Foix, Karine Seaudeau-Pirouley, Patrick Lacroix-Desmazes, Promising polymer-assisted extraction of palladium from supported catalysts in supercritical carbon dioxide, Journal of CO2 Utilization, 41 (2020), 101232, IF=5.993, RIS=2.868 https://www.sciencedirect.com/science/article/pii/S2212982020301359

Obtained results Stage 4 2021

• Report (Stage 4)
• Participation at videomeetings (19.01.2021, 21.04.2021, 07.07.2021, 10.09.2021, 04.10.2021)
• Published ISI paper:
  • Andrea Ruiu, Bernhard Bauer-Siebenlist, Marin Senila, W. S. Jennifer Li, Karine Seaudeau-Pirouley, Patrick Lacroix-Desmazes, Thorsten Jänisch, Supercritical CO2 Extraction of Palladium Oxide from an Aluminosilicate-Supported Catalyst Enhanced by a Combination of Complexing Polymers and Piperidine, Molecules, 2021, 26, 68, Factor de impact = 4.411, RIS=1.314.
    https://www.mdpi.com/1420-3049/26/3/684
• Participation at scietific events
  • Marin Senila, Oana Cadar, Bernhard Bauer-Siebenlist, Sarah Böringer, Karine Seaudeau-Pirouley, Patrick Lacroix-Desmazes, “Characterization of materials resulted form spent automotive catalysts using spectrometric techniques”, 6th Ed. Smart Materials and Surfaces, 20-22 Octomber 2021, Milano, Italy (on-line conference), poster presentation.
  • Patrick Lacroix-Desmazes, Andrea Ruiu, Karine Seaudeau-Pirouley, Marin Senila, Sarah Böringer, Bernhard Bauer-Siebenlist “SUPERMET Project: Recovery of Precious Metals from Spent Catalysts by Supercritical CO2 Extraction Assisted by Polymers”, Workshop organised by French Cluster specialized in Chemistry: AXELERA, 29 June, 2021.

Project start 01/05/2018

Project end 30/10/2021

Project duration 42 months

Number of Romanian institutions: 1

Budget

National funds 489.061,00 RON

Co-financing 0,00 RON

EC funds: 134.289,00 RON

Total budget: 623.350,00 RON

Contact

Dr. Marin Senila, Senior Researcher
Str. Donath nr. 67, Cluj-Napoca, Romania
E-mail: marin.senila@icia.ro; icia@icia.ro
Tel/Fax: +40 264 420590 / +40 264 667

Useful link:

https://supermetproject.eu/

Documents

Press release

Participation at scietific events

1. M. Senila, O. Cadar, T. Jänisch, P. Lacroix-Desmazes, “Method Validation for Determining Platinum and Palladium in Catalysts using Inductively Coupled Plasma Optical Emission Spectrometry”, International Conference on Analytical Chemistry and Applied Spectroscopy (ICACAS 2019), June 20-21 2019, Venice (Italy).
2. P. Lacroix-Desmazes, A. Ruiu, K. Seaudeau-Pirouley, M. Senila, T. Jänisch, B. Bauer-Siebenlist, “SUPERMET project”, Proceedings – Journées Nationales Supercritiques 2018 (JNSC2018), December 4-5, 2018, Toulouse (France).
3. P. Lacroix-Desmazes, A. Ruiu, K. Seaudeau-Pirouley, M. Senila, T. Jänisch, B. Bauer-Siebenlist, “SUPERMET project : Recovery of Precious Metals from Spent Catalysts by Supercritical CO2 Extraction Assisted by Polymers”, Proceedings – International Symposium on Green Chemistry (ISGC 2019), May 13-17, 2019, La Rochelle (France).
4. A. Ruiu, K. Seaudeau-Pirouley, M. Senila, T. Jänisch, B. Bauer-Siebenlist, P. Lacroix-Desmazes, “SUPERMET project: recovery of precious metals from spent catalysts by supercritical CO2 extraction assisted by polymers”, Proceedings – European Polymer Federation Congress (EPF2019), June 9-14 2019, Hersonissos, Creta (Grece).
5. P. Lacroix-Desmazes, A. Ruiu, K. Seaudeau-Pirouley, M. Senila, T. Jänisch, B. Bauer-Siebenlist, “SUPERMET project: supramolecular assembly for the recovery of precious metals from spent catalysts by supercritical CO2 extraction”, Proceedings – International Polymer Colloid Group Conference (IPCG 2019), June 23-28 2019, Singapur.

Code

COFUND-ERANET-ERAMIN-MINTECO
Contract no: 52 / 2018

Title

Integrated eco-technology for a selective recovery of base and precious metals in Cu and Pb mining by-products

Acronym

MINTECO

Domain

4 – Eco-nano-technologies and advanced materials

Contracting authority

Executive Unit for Financing Higher Education, Research, Development and Innovation (UEFISCDI)

Participating institutions

1. BRGM (France) – Coordinator
   
2. National R&D Institute for Nonferrous and rare Metals (Romania)
   
3. National R&D Institute in Optoelectronics INOE 2000 (Romania)
   
4. Eskisehir Osmangazi University (Turkey)
   
5. Romaltyn Mining SRL (Romania)
   
6. Mineral and Energy Economy Research Institute of the Polish Academy of Sciences (Poland)
   
7. Team Group Metals (Poland)
   
8. AJELIS (France)
   

Abstract

The MINTECO project aims to develop an integrated innovative, efficient and ecological technology for the recovery of base (Cu, Pb, Zn) and precious (Au, Ag) metals from Cu and Pb bearing mining waste (CLBM). The project will allow the establishing of a global management methodology to treat historical mining sites and to reduce disposed volumes of metal-bearing waste. The MINTECO project will be tested on a selected case study on CLMB (3 mining sites identified in Romania, Poland and Turkey) by using pre-concentration methods (mineral processing) to separate non-useful compounds contained in the coarse fractions followed by leaching of concentrated fractions to dissolve all targeted metals and their recovery by innovative techniques (using dedicated synthesized organic molecules, thiosulfates and ionic liquids). The main steps (pre-concentration/ leaching/ high grade metal recovery) will be studied in detail by research institutes to optimize first relevant process sequences. Then, a global coherent flowsheet will be proposed and the developed technologies will be subsequently validated by the industrial partners (SMEs) in the project at TR>4. Also, a final economic and environmental assessment will be performed. The consortium gathers 8 partners from 4 countries (France, Romania, Poland and Turkey) and is composed of 3 research institutes,1 university, 1 public institution and 3 SMEs with complementary expertise.

Project objective

The global objective of the MINTECO project is the development of an integrated innovative, efficient and ecological technology for the recovery of base and precious metals from copper and lead bearing mining wastes. The project will allow the establishing of a management strategy to treat and reduce disposed volumes of high metal content waste and plans to contribute to the reduction of Europe’s dependence on raw material imports. Also, the project targets the reduction of polluted emissions to air, soil, and water.

Estimated results

• Report on waste characterization.
• Methods selected for selective extraction of Au and Ag from waste.
• Experimental results on Au and Ag selective extraction method.
• Experimental results on Au and Ag electrochemical separation method.
• Separation and recovery procedure for Au and Ag.
• Laboratory technology project for Au and Ag recovery.
• Environmental impact study of Au and Ag recovery technology.
• Communication – international conference.
• Optimized Au and Ag separation and recovery method.
• Laboratory technology for Au and Ag recovery.
• Cost-benefit analysis of the recovery technology.
• Article (sent for publication).
• Communication (international conference).
• Assessment study on the recovery technology.
• Minute of consortium meetings.

Project start 01/05/2018

Project end 31/10/2021

Project duration: 42 months

Number of involved institutions (Romanian): 3

Budget

National funds 321085,00 RON

Co-financing 0,00 RON

EC funds: 88217,00 RON

Total project budget: 409502,00 RON

STAGE 1 (2018).

A1.1 Characterization of meatal-bearing mining wastes
A1.2 Assessment of selective extraction methods for Au and Ag
A1.3 Consortium meetings

RESULTS

• Representative meatal-bearing mining wastes from Baia-Mare mining site
• Composition of wastes
• Method for Au şi Ag extraction
• Minute of Kick-off meeting
• Minute of Conf-Call November 2018
• 1 published paper
• 1 conference presentation
• Project web page

Paper: Emilia Neag, Maria-Alexandra Hoaghia, Anamaria Török, Erika Levei, Marin Șenilă, Cecilia Roman, Study of metals leaching from nonferrous mine tailings in organic and inorganic extractants, International Journal of Chemistry and Chemical Engineering Systems, ISSN: 2367-9042, Volume 3, 2018, pag. 42-49

Conference: Emilia Neag, Maria-Alexandra Hoaghia, Anamaria Török, Erika Levei, Marin Șenilă, Cecilia Roman, Study of metals leaching from nonferrous mine tailings in organic and inorganic extractants, ISMAEDEH ’18, 6th International Conference on Integrated Systems and Management for Energy, Development, Environment and Health, Rome, Italy, November 23-25, 2018

Stage 2 (2019)

A2.1. Experiments for Au and Ag selective extraction
A2.2. Electrochemical tests for Au and Ag selective extraction
A2.3. Tests for Au and Ag separation and recovery
A2.4. Lab scale technology for Au and Ag recovery –flowchart
A2.5. Assessment of the technology impact on the environment
A2.6. Results dissemination. Consortium meetings.

RESULTS

• Report (stage 2)
• Procedure for the recovery of Au and Ag from tailings
• Flowsheet of the lab scale technology for the recovery of Au and Ag from tailings
• Minute of the Progress meeting (Krakow, Poland, 26-27 March 2019)
• Minute of the Conf Call 19 September 2019
• 2 conference presentations

Stage 3 (2020)

A3.1. Optimization of the Au and Ag separation and recovery method.
A3.2. Lab-scale technology for the Au and Ag recovery
A3.3. Assessment of the costs and benefits of the lab-scale technology for the Au and Ag recovery
A3.4. Results dissemination. Consortium meetings.

RESULTS

• Report (stage 3)
• Optimized Au and Ag separation and recovery method
• Lab-scale technology for the Au and Ag recovery
• Report on the costs and benefits of the lab-scale technology for the Au and Ag recovery
• Meeting minutes (11.02.2020, 03.06.2020, 09.11.2020)
• 1 conference presentation
• 1 book chapter

Participation at scietific events

1. E. Levei, C. Varaticeanu, E. Neag, M. Bizo, M. Ghiță, F. Bodénan, Recovery of gold and silver from mining tails by ammonium thiosulphate leaching, 2nd International Conference on Emerging Technologies in Materials Engineering, 6-8 November 2019, Bucharest, Romania- poster
2. J. Bodin, N. Menad, F. Bodénan, E. Levei, M. Bizo, M. Ghita, Evaluation of mineral processing techniques to concentrate metals (Pb, Zn, Cu, Au) in mining residues at Baia Mare, Romania, 2nd International Conference Mines of the future, 12-14 June 2019, Aarhen, Germany – poster
3. Ghita Mihai, Bodenan Francoise, Levei Erika A., Kulczycka Johanna, Muammer Kaya, Shilova Ekaterina, Bizo Mircia, Development of efficient laboratory technologies for selective recovery of base and precious metals from Cu and Pb mining by-products, 4th edition of Research and Innovation Fair, UGAL INVENT 2017, Dunărea de Jos” University, 16-18 OCT 2019 Galaţi, Romania
4. Erika Andrea Levei, Cerasel Varaticeanu, Emilia Neag, Simion Bogdan Angyus, Jack Goldstein, Rozica Osanu, Mircia Bizo, Mihai Ghita, Francoise Bodenan, Eco-friendly technology for gold recovery from Cu and Pb bearing mining waste, 3rd International Conference On Emerging Technologies In Materials Engineering EmergeMAT, 29-30 Octombrie, Bucuresti, Romania – poster

Book chapter

1. Emilia Neag, Eniko Kovacs, Zamfira Dinca, Anamaria Iulia Török, Cerasel Varaticeanu and Erika Andrea Levei, Hydrometallurgical recovery of gold from mining wastes, in Solid Waste Management, Ed. Hosam El-Din Saleh, IntechOpen, London, UK, 2020, DOI: 10.5772/intechopen.94597. https://www.intechopen.com/online-first/hydrometallurgical-recovery-of-gold-from-mining-wastes

Stage 4 (2021)

• A4.1. Comparative assessment of the technology for Au and Ag recovery using ammonium thiosulphate with other technologies.
• A4.2. Results dissemination. Consortium meetings.

Results

• Report (stage 4)
• Study of the technology for Au and Ag recovery using ammonium thiosulphate in comparison with other technologies
• Sudiu cu privire la evaluarea comparativa a tehnologiei de recuperare a Au si Ag folosind extractia in tiosulfat de amoniu in prezenta aminei cuprice cu alte tehnologii similare
• Webinar flyer
• Meeting minutes (12.03.2021, 16-17.09.2021)
• 1 paper published in WoS indexed journal
• 1 conference presentation
• Papers in journals indexed in WoS:
  • Emilia Neag, Anamaria Iulia Török, Zamfira Dincă, Marin Senila, Cerasel Varaticeanu, Erika Andrea Levei, Ekaterina Shilova, Francoise Bodenan, Optimization of gold sorption from ammoniacal thiosulphate solution (2021), STUDIA UBB CHEMIA, LXVI, 2, 151-161 http://chem.ubbcluj.ro/~studiachemia/issues/chemia2021_2/13Neag_etal_151_161.pdf
• Participation at scietific events
  • Johanna Kulczycka, Ewa Dziobek, Lukasz Lelek, Erika-Andrea Levei (2021) The benefits of recovering metals from mining waste. Case of Romania, Online conference: Young Researchers’ Innovative Ideas: Science| Start-Ups| Industry, Krakow, Poland (27-28 May 2021)

Webinar

• Invitation
• Click to join

Contact

Project manager
CSI Dr. Erika Levei
Str. Donath nr. 67, Cluj-Napoca, Romania
E-mail: erika.levei@icia.ro; icia@icia.ro
Tel/Fax: +40 264 420590 / +40 264 420667