Substantia. An International Journal of the History of Chemistry 3(1) Suppl.: 61-66, 2019 Firenze University Press www.fupress.com/substantia Citation: A. Serpe (2019) Hi-Tech waste as “Urban Mines” of precious metals: new sustainable recovery methods. Substantia 3(1) Suppl.: 61-66. doi: 10.13128/Substantia-607 Copyright: © 2019 A. Serpe. This is an open access, peer-reviewed article published by Firenze University Press (http://www.fupress.com/substantia) and distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distri- bution, and reproduction in any medi- um, provided the original author and source are credited. Data Availability Statement: All rel- evant data are within the paper and its Supporting Information files. Competing Interests: The Author(s) declare(s) no conflict of interest. ISSN 1827-9643 (online) | DOI: 10.13128/Substantia-607 Hi-Tech waste as “Urban Mines” of precious metals: new sustainable recovery methods Angela Serpe Department of Civil and Environmental Engineering and Architecture (DICAAR) and INSTM unit, Via Marengo 2, I09123 Cagliari, Italy E-mail: serpe@unica.it. Phone N.: +39 0706755543. Abstract. Precious metals (PMs) are valuable components of Hi-Tech goods such as electrical and electronic equipment, catalysts, advanced materials. These relatively recent applications and the growth of their market due to the fast technological devel- opment, heavily contribute to the high rate of element consumption and Hi-Tech waste accumulation of the modern consumer society. Looking at these wastes with new eyes, encouraged by the recent world-wide regulations aimed to the sustainable waste man- agement and raw materials preservation, we can appreciate the value contained in and turn them in secondary resources of raw materials. In this context, a sustainable approach in PMs recovery from Hi-Tech waste, built on green chemistry principles and addressed to find a ready technological transfer, is described here. Keywords. Green processes, circular economy, secondary sorces, noble metals recov- ery, waste electrical and electronic equipments. OVERVIEW One of the main aspects related to the modern consumer society is the fast technology development and the inevitable production of high and increasing amount of waste it entails. The assets, especially the Hi-Tech ones, play an essential role in our daily life and their life cycle gradually decreases. Electronic equipment, automotive devices and advanced materi- als, often contain significant quantities of valuable and even toxic materials which would be destined to landfill, thus generating a serious environmen- tal issue, if not valorized in a different way, e.g. through reuse or recycling. European and several other countries regulations on Waste Electrical and Electronic Equipment (WEEE),1,2 End-of-Life Vehicles (EoLV)3 and bat- teries & accumulators,4 the fastest growing and pollution generating waste streams in the world, ban the uncontrolled disposal of these goods at the end of their life encouraging the implementation of a virtuous circular economy model where the recovered materials, obtained as output of waste valorization processes, are the input raw materials for new productions.5–7 Sustainable recovery processes are also urged in order to prevent pollution and further waste generation. 62 Angela Serpe In this context, PMs play a key role. Indeed, they are widely used in Hi-Tech goods because of their physi- cal and physicochemical properties. High electrical and thermal conductivity and high resistance to the oxidation (they belong to the noble metals family characterized by high reduction potentials), coupled with their malleability and ductility, make these materials particularly appeal- ing for industrial application mainly as conductors in long lasting high technologies. Besides that, they have limited natural availability and high economic value. For these reasons, and due to the relatively high PMs concentration in Hi-Tech scraps (where often they are present in con- centration even higher than in their ores),8,9,10 their recov- ery may represent the driving force for the profitability of more comprehensive materials recovery processes. Currently the main methods used industrially to recover valued metals from the main Hi-Tech wastes have been mostly inherited from the well-known processes conventionally applied on ores and jewelry ashes and are mainly based on pyrometallurgy and hydrometallurgy.11,12 The former, which operates by smelting and refining, gen- erates high financial and environmental costs, while the latter, less energy-intensive, more tunable and predictable but often based on the use of toxic and aggressive sub- stances (e.g. cyanides, strong oxidizing acids), can heavily affect the environment, biodiversity and human health, if not strictly controlled for reactants and wastewaters pro- duction. A wide research effort is hence required to find new ways for recovering and recycling materials from Hi-Tech scraps able to combine effectiveness to environ- mental sustainability. A multidisciplinary environmental science approach is needed to face this challenge. The last two decades have seen environmental scientists with dif- ferent background (e.g. chemists, engineers, biologists) and complementary skills, at work for turning this issue into a market, scientific and environmental opportunity. Some interesting results, both in terms of effectiveness and envi- ronmental sustainability, have been obtained in the last two decades by Deplano’s group of coordination chemists, for gold, palladium and platinum recovery from Hi-Tech wastes by using safe leaching agents and mild condition processes.13 Here we describe the results obtained for two different families of Hi-Tech waste, following a new green- er approach, exploiting the interaction between the com- plexing and oxidizing species in the reaction environment which promotes an effective NMs leaching. THE CASE OF WEEE The WEEE family contains all the devices that work with electric current or electromagnetic fields, such as: personal computers, mobile phones, TVs, printers, refrigerators, washing machines, photovoltaic panels, lamps and other small and large appliances. This type of waste contains a variety of different materials that stimulate interest on recycling profitability. At the same time, they make recovery processes a really complex issue. In particular they can contain plastics, glass, cop- per, aluminum, iron, as well as noble materials, especial- ly metals (e.g. gold, silver, palladium), and other critical elements such as “rare earths”, often beside toxic sub- stances such as mercury, cadmium and lead, extremely hazardous for the environment and for human health. To understand the greatness of the WEEE phenom- enon, it is worth mentioning that world production of WEEE in 2016 was around 45 million tons (+8% by 2014). According to the ONU, this trend is expected to grow further to 52.2 million tons (+17%) by 2021, the fastest increasing rate in the world’s solid urban waste.14 But there is still much to do for turning them into val- ue, recovering materials in an environmentally friendly manner differently from currently used industrial meth- ods. Conventional methods often give a not satisfactory (in terms of recovery rates) and costly (both in terms of economic and environmental impact) answer to this need. An interesting promising contribution in the field of NMs recovery from WEEE - in particular small appli- ances, Printed Circuit Boards (PCBs), printer cartridges and smartcards - comes from the smart use of coordi- nation chemistry in finding sustainable reactants able to combine oxidizing and complexing properties in a single molecule. It is well-known, indeed, that the presence of a complexing agent is necessary to lower the reduction potential and make feasible the oxidation of metals with highly positive reduction potential such as gold, palla- dium and platinum (as in the case of cyanides and aqua regia).11 Molecules coupling complexing and oxidiz- ing moieties show enhanced reactivity with respect of the “free” reagents, as demonstrated in the 1990s by the McAuliffe’s group in a pioneering study on the reactiv- ity of R3D·I2 (R = Alkyl; D= As, P) Charge-Transfer (CT) complexes towards crude inactivated metal powders.15 On these basis, with the view to find safer and more effective leaching agents able to overcome the sustain- ability issues put by conventional methods, Deplano’s group started an extensive study on the use of sulfur- donor/dihalogen CT complexes. In particular, dihalo- gen/interhalogen adducts of cyclic and acyclic dithiooxa- mides (DTO), soft chelating ligands bearing two vicinal thionic groups able to favor the square planar geometry preferred by d8 metal ions, demonstrated to be a power- ful class of non-cytotoxic and easily handled lixiviants towards gold,13,16,17,18 palladium,13,19 copper,13 silver,13,21 63Hi-Tech waste as “Urban Mines” of precious metals: new sustainable recovery methods and platinum,22 under very mild conditions, mainly pro- viding complexes of general formula [M(DTO)2]n+ and/ or [M(DTO)I2](n-2) (M = NM; n = charge of the metal cation) as shown in Table 1. Among them, the bis-diiodine adduct of the N,N’- dimethyl-perhydrodiazepine-2,3-dithione (Me2dazdt·2I2) behaved as the most effective in the one-pot gold dis- solution at room temperature and pressure in common organic solvents, and it was employed fully satisfactorily for the sustainable gold recovery phase in WEEE treat- ments as patented by the group in the last decade for the lab scale.23,24 Figure 1 summarizes the patented three- step sustainable process for the treatment of a test speci- men consisting in a thin metal powder (diameter=0.4mm) obtained by small appliances and PCBs comminution and deprived by aluminum, ferrous metals and vitreous-plas- tic materials, consisting in the selective dissolution and recovery of i) base metals; ii) copper; iii) gold. The described process is based on the use of safe reagents. It is selective and easy to be implemented and managed consisting in just few steps which require mild operative conditions. Moreover, it is effective in the recovery of noble metals, which are obtained almost quantitatively in form of elemental metal by chemi- cal (cementation) or electrochemical (electrowinning) reduction. From the other side, Me2dazdt·2I2, though recyclable at the end of the process, is a reagent not yet available on the market and which works in organic sol- vent. In order to promote green chemistry processes able to meet green engineering principles as well for a faster technology transfer on industrial scale,11,25,26 several changes in the process were studied and implemented as improvements. In particular: – 1st step: a refluxing citric acid solution was used in place of HCl, in order to promote the use of weaker natural acids and increase selectivity; – 2nd step: an alkaline I-/IO3- mixture, able to combine oxidizing with coordinative capability, was used, in the presence of ammonia, as a more reliable alterna- tive to H2O2, avoiding effervescence phenomena and promoting in one time the copper leaching and the separation of silver from the solution in form of AgI precipitate; – 3rd step: a I2/I- water solution was used as leach- ing agent for gold in turn of the Me2dazdt·2I2 solu- tion in organic solvent. Although the demonstrated lower reactivity of the I2/I- mixture, the lower cost of the reagents, their availability on the market and, remarkably, the easy recyclability of I2, make this process really promising for a sustainable applica- tion on a large scale. Satisfactory results (almost quantitative yields in NMs recovery) were obtained on the cited test specimen through this new process design, pursuing a virtuous cycle able to limit the wastewater production.27 Remark- ably, this process demonstrated to be applicable satisfacto- rily also on coarser materials like shredded PCBs, where a heterogeneous size distribution and the presence of com- posite materials are present.28 These last results demon- strate the robustness of the approach which seems appeal- ing also from a costs/benefits ratio point of view(1) and open the way for further larger scale experimentations. 1 The mechanical comminution and separation pre-treatments of the incoming material represent one of the heaviest costs of the whole recovery process Table 1. Summary of the reactions between cyclic dithioxamides/I2 leaching agents and Au, Pd, Pt, Ag, Cu powders under mild con- ditions: room temperature, 2:1 molar ratio; acetone (or THF or CH3CN). Leaching agent Metal Main product Ref. Au [Au(Me2dazdt)I2]I3 13,16,17 Ag -a 13 Pd [Pd(Me2dazdt)2]I6 13,19 Pt -b 13 Me2dazdt·2I2 Cu [Cu(Me2dazdt)2]I3 13 Au [Au(Me2pipdt)I2]I3 13 Ag [Ag(Me2pipdt)I]2 13,20 Pd [Pd(Me2pipdt)2]I6 13 Pt [Pt(Me2pipdt)2]I6c 22 [HMe2pipdt]I3 Cu [Cu(Me2pipdt)2]I3 13 aUnidentified product; bunreacted metal; cobtained under solvent reflux. Figure 1. Schematic representation of the Deplano’s group Cu and Au recovery method from comminuted WEEE, based on the use of Me2dazdt·2I2 as gold leaching agent.22,24 64 Angela Serpe THE CASE OF THREE WAY CATALYSTS (TWCS) TWCs are exhaust emission control devices applied to the exhaust of vehicles in order to significantly reduce the polluting emissions (essentially of CO, unburnt hydrocarbons and NOx), favoring oxidation and/or reduction reactions with formation of non-harmful compounds. Thanks to modern regulations that impose strict limits on vehicles emissions, from the 1st Janu- ary 1993 the use of TWC is mandatory for all cars in all European countries. Every year, between 6 and 7 mil- lion of EoLV, corresponding to 7 and 8 million tonnes of waste, are generated in the European Union which should be managed correctly. Well-known procedures for managing EoLV, reuse of still working parts and processes for the enhancement of bulky materials such as iron, aluminum, glass, etc., have being implemented. Differently, it is still an issue to enhance materials from electronic apparatus, batteries, car fluff (complex mix- ture of non-ferrous materials including plastics, foam, textiles, rubber and glass residue from car demanufac- turing) and catalytic converters. Among them, in the specific field of noble met- als reclamation, catalytic converters represent a rare opportunity. Indeed, they typically consists in a metal case containing the substrate (ceramic or metallic, with a “honeycomb” structure) coated by the wash-coat(2) which supports from 5 to 8g (for petrol and diesel engines, respectively) of highly dispersed catalytically active phase formed by a mix of metal platinum, pal- ladium and rhodium. These metals are able to promote the oxidation of carbon monoxide to carbon dioxide and that of unburnt hydrocarbons to carbon dioxide and water (Pd and Pt), and the reduction of nitrogen oxides to nitrogen (Rh).29 Notably, Pd-only technology has been introduced in catalytic converters in the last years.30 It is estimated that the car industry alone, which puts about 40 million new cars on the market every year, represents a potential annual resource of $1 billion of Pd recov- ery.29 Currently significant but still low (∼30%) noble metals recycling from spent car converters29 is done by non-selective unattractive methods involving unselec- tive pyrometallurgical chlorination30 or dissolution with strong oxidizing acids30 in the crucial metal-dissolution step.31,32 Based on the promising results described above on the use of dithioxamide/I2 adducts with crude met- al palladium, a joint project by Deplano’s group, from University of Cagliari, and Graziani’s group, from Uni- versity of Trieste, allowed to check the effectiveness of Me2dazdt·2I2 on model TWCs consisting in a Pd(2.8%)- 2 High specific surface layer 40-50 mm thick, of g-alumina or CeO2– ZrO2/Al2O3 in current technologies CeO2–ZrO2/Al2O3 material underwent simulated aging (1050°C, 200h) for assessing its potential in Pd recovery from spent car converters.33,19 Almost quantitative Pd- dissolution and recovery rates were achieved through the selective metal leaching by refluxing a Methyl Ethyl Ketone (MEK) solution of the molecular adduct in the presence of the cited test specimen in form of powder for 168 hours, has been patented and summarized as follows (Figure 2). The main recovered product was the [Pd(Me2dazdt)2] I6 complex. Pd metal was quantitatively obtained by both chemical and thermal degradation of the molecular compound. Differently, Pd metal recovery attempts by chemical or electrochemical reduction were unsuccess- ful as expected because of the dithiolenic nature of the dicationic compound.(3) Nevertheless, [Pd(Me2dazdt)2] I6 complex demonstrated to be successfully applicable in his molecular form as valuable homogeneous catalyst for C-C coupling reactions34 and as precursor of effective photo-catalysts for H2 production.35 As a cheaper alternative, we recently studied the use of safe fully organic triiodides (organic cations: tetrabut hylammonium, TBA+; tetraphenilphospho- nium, Ph4P+; 3,5-bis(phenylamino)-1,2-dithiolylium, (PhHN)2DTL+) as Pd leaching agents in organic sol- vents. The presence of an organic cation in the triiodide salt showed to dramatically improve its Pd-leaching properties with respect to those of the fully inorganic KI3 salt, hampering the formation of PdI2 coating pas- sivation (typically present in these cases and limiting the leaching reaction to go ahead) by promoting the formation of stable and soluble ionic couples of gen- 3 In this class of complexes, the reduction event involves the whole mol- ecule without achieving dissociation into metal and ligand components. Figure 2. Schematic representation of the Deplano’s group Pd recovery method from model aged TWCs based on the use of Me2dazdt·2I2 as palladium leaching agent.33 65Hi-Tech waste as “Urban Mines” of precious metals: new sustainable recovery methods eral formula Org2[Pd2I6].36 Although the recovery rates achieved using the cited triiodide salts were found slightly lower than those found by Me2dazdt·2I2 solu- tions in analogous experimental conditions (98%, 83%, 73% for (PhHN)2DTLI3, Ph4PI3 and TBAI3, respectively, vs almost quantitative for Me2dazdt·2I2), these reactants seem really appealing for practical application due to their low cost and environmental impact, mild reaction conditions, market availability (or easy synthetic pro- cedures), as well as for the easy metal Pd and reagents recyclability. CONCLUSIONS AND PERSPECTIVES The present work highlights how coordination chemistry, which is traditionally involved in the recov- ery/refining processes of NMs, can give a relevant con- tribution in designing molecular-level methods able to combine effectiveness with low environmental impact, as promoted by green chemistry principles and required by new legislation. On these basis multidisciplinarity seems the key approach to grew up molecular to industrial scale processes meeting both green chemistry and engi- neering requirements in order to balance sustainabil- ity with economic development. Here, a new promising sustainable approach based on the combined coordina- tive and oxidizing capability of safe, easy to handle and working in mild conditions charge-transfer compounds towards NMs, has been presented. A further effort is required to the Environmental Sciences community for implementing these methods on a larger scale in order to promote the conversion of Trash into Resource mak- ing the “circular economy” model feasible. ACKNOWLEDGEMENTS The author thankfully acknowledges TCA for the kind invitation to present this work at the “I Metalli Preziosi nella Storia della Scienza e della Tecnologia” symposium in the occasion of the goldsmith fair 2018 in Arezzo.37 It is worth to mention that the work described here has been carried out by valuable research groups in around 30 years of research activity. The author thank- fully acknowledges professor Paola Deplano for design- ing and coordinating the research activity at University of Cagliari and for mentoring the author and the other co-workers on this topic for the future developments. The author also acknowledges professors Mauro Grazi- ani and Paolo Fornasiero and their co-workers, Univer- sity of Trieste, for their relevant contribution in studying the TWCs applications and the photo-catalytic behavior of the Pd-complex in H2 production, as well as profes- sor Massimo Vanzi and co-workers, University of Cagli- ari, for WEEE characterization and professor Luciano Marchiò, University of Parma, for X-Ray characteriza- tion and theoretical calculations on ligands and com- plexes. Sardegna Ricerche, University of Cagliari, 3R Metals Ltd and the companies supporting the project “#Recovery #Green #Metal”, are greatly acknowledged for financing and supporting the research on metal recovery from Hi-Tech waste and the technology trans- fer of the research results. 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Serpe, ACS Sustainable Chemistry and Engineering, 2017, 5, 4359–4370. 37 Precious Metals in the History of Science and Tecch- nology, https://eventotcametallipreziosi.it/ Substantia An International Journal of the History of Chemistry Vol. 3, n. 1 Suppl. - 2019 Firenze University Press The Arezzo seminar on precious metals Iacopo Ciabatti1, Marco Fontani2, Carla Martini3 Apprentices and masters - the transmission of ancient goldsmith techniques Alessandro Pacini The authenticity of the false Daniela Ferro Electrodeposition and innovative characterization of precious metal alloys for the Galvanic and Jewel industry Massimo Innocenti, Walter Giurlani, Maurizio Passaponti, Antonio De Luca, Emanuele Salvietti Gold and silver: perfection of metals in medieval and early modern alchemy Ferdinando Abbri “Antichi Strumenti Orafi” of the Garuti Collection – The Virtual Exhibition Francesca Frasca1, Adelmo Garuti2, Gian Lorenzo Calzoni3 Do monetary systems rediscover precious metals in the era of ‘bitcoins’? Roberto Santi Gold parting with nitric acid in gold-silver alloys Iacopo Ciabatti Hi-Tech waste as “Urban Mines” of precious metals: new sustainable recovery methods Angela Serpe