Recycling of platinum group metals from the used auto catalytic converters is profitable from ecological and also economical point of view. This work presents the analysis of the chances of removing the platinum group metals (PGM) from the used auto catalytic converters applying pyrometallurgical and hydrometallurgical methods. The characteristics of auto catalytic converter is shown as well the available technologies used for processing the auto catalytic converters are also presented.Recikliranje metala iz grupe platina od korištenih automobilskih katalitičkih konvertera je profitabilno s ekološkog i također s ekonomskog stajališta. Ovaj rad prezentira analizu mogućnosti izdvajanja metala iz grupe platina od korištenih automobilskih katalitičkih konvertera uz primjenu pirometalurških i hidrometalurških metoda. Prikazane su karakteristike automobilskih katalitičkih konvertera kao i raspoložive tehnologije koje su korištene za obradu automobilskih katalitičkih konvertera

A. Fornalczyk

M. Saternus

English

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A. FORNALCZYK, M. SATERNUSREMOVAL OF PLATINUM GROUP METALSFROM THE USED AUTO CATALYTIC CONVERTERReceived – Prispjelo: 2008-06-22Accepted – Prihva}eno: 2008-09-10Review Pages – Pregledni radINTRODUCTIONMilions of cars that drive every day on the roads arethe source of pollution to the air. This is especially ob-served in the big cities and urbanized areas. The averagefamily car would emit 15 Mg of the toxic and harmfulpolluting gases over a 10 year life period 1. These pol-luting gases can be reduced by catalytic converters (re-move 98 % of pollution).Therefore, current legislation establishes standardsthat require the fitting of catalytic converters to all newcars. The first countries that established such standardswere USA and Japan. Then this legislation came intoforce in Europe, Australia and parts of Asia in the 1980s,followed in the 1990s by the developing economies ofBrazil, Mexico and India 2.It is estimated that this regulations have preventedemission of 12 billion Mg of harmful polluting gases tothe air 3. Today over half of the world's 500 millioncars are fitted with a catalytic converters.CHARACTERISTICOF AUTO CATALYTIC CONVERTERSAn auto catalytic converter (Figure 1) reduces theemission of harmful gases, such as carbon monoxide,hydrocarbons and nitrogen oxides. During the catalyticprocess these gases are transformed into carbon dioxide,water, and nitrogen. The following chemical reactioncan be written:2CO + O2 = 2CO2 (1)2C2H6 + 7O2 = 4CO2 + 6H2O (2)2NO + 2CO = N2 + 2CO2 (3)Most modern cars are equipped with three-way cata-lytic converters. This refers to the three regulated emis-sions it help to reduce their harmfulness.Large active surface of catalytic converter is a neces-sary condition for its efficient working. This surface iscreated by the carrier with a honeycomb structureMETALURGIJA 48 (2009) 2, 133-136 133Recycling of platinum group metals from the used auto catalytic converters is profitable from ecological andalso economical point of view. This work presents the analysis of the chances of removing the platinum groupmetals (PGM) from the used auto catalytic converters applying pyrometallurgical and hydrometallurgical met-hods. The characteristics of auto catalytic converter is shown as well the available technologies used for proces-sing the auto catalytic converters are also presented.Key words: auto catalytic converter, PG metals, platinum removalIzdvajanje metala iz grupe platina iz kori{tenih automobilskih kataliti~kih convertera. Recikliranjemetala iz grupe platina od kori{tenih automobilskih kataliti~kih konvertera je profitabilno s ekolo{kog i tako|ers ekonomskog stajali{ta. Ovaj rad prezentira analizu mogu}nosti izdvajanja metala iz grupe platina od kori{te-nih automobilskih kataliti~kih konvertera uz primjenu pirometalur{kih i hidrometalur{kih metoda. Prikazane sukarakteristike automobilskih kataliti~kih konvertera kao i raspolo`ive tehnologije koje su kori{tene za obraduautomobilskih kataliti~kih konvertera.Klju~ne rije~i: auto kataliti~ki konverter, GP metali, izdvajanje platineISSN 0543-5846METABK 48(2) 133-136 (2009)UDC – UDK 669.23:629.113:541.128=111A. Fornalczyk, M. Saternus, Faculty of Materials Science and Metallurgy,Silesian University of Technology, Katowice, Poland Figure 1. View of an auto catalytic converter(Figure 2) and the catalytic system. Carrier consists of aceramic or metallic substrate coated by an aluminiumoxide (Al2O3) with other rare earth oxides such as CeO2,ZrO2. Platinum group metals (platinum, palladium, rho-dium) are responsible for the catalytic function.Platinium is responsible for transforming hydrocar-bons and carbon monoxide to water and carbon dioxide,while rhodium is most efficient in reducing nitrogen ox-ides to nitrogen. Palladium can handle all three pollut-ants, but less efficiently than platinium or rhodium. Die-sel oxidation catalytic converters contain no rhodium.Today’s exhaust systems are characterized by an in-creased complexity, as one distinguishes oxidation cata-lysts and three-way catalysts for gasoline engines, NOxadsorbers for lean-burn engines, particulate filters andoxidation catalysts for diesel engines, aside from selec-tive catalytic reduction units and NOx adsorbers for die-sel and many others 4.PGM DEMANDS AND SUPPLIESPGM (Pt, Pd, Rh) are used in auto catalytic convertersdue to their remarkable resistance to high temperaturecorrosion and oxidation. The quantity of platinum, palla-dium and rhodium used in auto catalysts may vary greatlyby vehicle type, manufacturer, country, year and addi-tional factors. For example depending on the engine ca-pacity the auto catalytic converters can contain about 1,5g of platinum, 0,3 g of rhodium and small amounts of pal-ladium 5, 6. In three-way catalytic converters the ratioof platinum and rhodium is 5 to 1 and the ratio of palla-dium and rhodium is 7 to 1. The contents of PGM rangesfrom 1,42 to 1,76 g for 1 dm3 of carrier capacity 5, 6.The demand for auto catalytic converters is still in-creasing 6, therefore the demand for PGM is expectedto grow in the nearest future. The driving force behindthis is the use of platinum in catalytic converters, partic-ularly those fitted to diesel vehicles. Tighter restrictionson the permissible levels of NOx in automotive exhaustcontinue to drive the demand for rhodium. Auto cata-lytic converters now account for over 87 % of the rho-dium used 6. Table 1 presents primary PGM (Pt, Pd,Rh) production, whereas Table 2 presents demand forPGM with special focus on using this PGM in auto cata-lytic converters.Table 2 also presents the value of recycled PGM. Itcan be observed that this value is getting higher everyyear.Table 1. Primary production of palladium, platinumand rhodium in the years 2001 – 2007 7Year Primary production / MgPd Pt Rh2001 227,7 182,3 18,82002 163,3 185,7 19,12003 200,6 192,8 22,52004 265,9 201,9 22,42005 261,4 206,5 23,52006 250,7 211,3 25,62007 258,8 207,1 25,0About 15 - 20 % of the world demand for platinumcomes recycling especially from the used auto catalyticconverters. However, this amount of platinum is notenough to meet the growing demand for this material(Table 1 and 2) 8. All these makes platinum reservesshrink and in consequence platinum prices increase (Ta-ble 3). For palladium and rhodium present situation ismore comfortable, production is, respectively, sufficientor nearly sufficient to meet the demands.The high value of PGM (Table 3) encourages recy-cling from scrap material especially coming from autocatalytic converters and is already successfully prac-tised. Table 4 shows the values of Pt and Pd recoveryfrom the used auto catalytic converters in different geo-graphical regions in the years 2001 - 2007. The NorthAmerica is the undisputed leader in this recovery.RECYCLING OF AUTOCATALYTIC CONVERTERSRecycling of PGM is very important because it pro-vides a supplementary source to the mining of thesemetals, therefore protecting environment by limiting thenumber of waste disposal, savings of natural resourcesexploitation, limiting the electricity consumption, di-minishing pollutant emission.At present in Poland there is no plant where PGMcan be recovered. The used auto catalytic converters arepurchased, collected and then imported to other coun-tries especially Germany. In the world there are somefirms which recover PGM metals from the used autoconverters. Umicore Autocatalyst Recycling is a goodexample of them. Its plants are presented in Table 5.At first the used auto catalytic converter for recy-cling must be prepared and homogenized. Then the rep-resentative sample is taken and analysis is done. If PGMcontents is below 30 %, pre-concentration is necessary.This can be done by incineration, by pyrometallurgicalconcentration or hydrometallurgical processes. The fol-134 METALURGIJA 48 (2009) 2, 133-136A. FORNALCZYK et al.: REMOVAL OF PLATINUM GROUP METALS FROM THE USED AUTO CATALYTIC CONVERTERFigure 2. The carrier auto catalytic converter with a ho-neycomb structurelowing stages are dissolution and PGM isolation and fi-nally PGM purification.PGM purification let to obtain very high puritymetal, but after all it is very expensive. It consumes largequantities of energy and can create dangerous solutions.Processes applied for PGM purification are the follow-ing: calcinations, ion exchange, (solvent)-extraction,hydrolysis, reduction and oxidation processes, precipi-tation 10.Figure 3 presents the main steps in PGM recoveryfrom the used auto catalytic converters, while Table 6shows some processes used to PGM recovery from autocatalytic convertersIn the hydrometallurgical methods PGM containedin the used auto catalytic converters were dissolved in anMETALURGIJA 48 (2009) 2, 133-136 135A. FORNALCZYK et al.: REMOVAL OF PLATINUM GROUP METALS FROM THE USED AUTO CATALYTIC CONVERTERTable 2. Demand for palladium, platinum and rho-dium and the value of recycled PGM fromauto catalytic converters 7Year Demand / Mg Recycled PGM (3)1) 2)Palladium2001 210,3 158,3 8,72002 150,5 94,9 11,52003 168,9 107,3 12,82004 204,0 117,9 16,52005 228,8 120,2 19,42006 201,2 125,7 24,92007 205,4 136,2 29,4Platinum2001 193,8 78,4 16,52002 201,2 80,6 17,62003 203,1 101,7 20,12004 203,4 108,6 21,52005 208,2 118,0 23,92006 209,3 128,8 26,62007 215,4 131,7 27,5Rhodium2001 18,0 17,6 2,72002 18,4 18,6 3,12003 19,3 20,5 3,92004 22,7 23,6 4,42005 25,7 25,8 4,32006 26,2 27,0 5,32007 25,1 26,8 5,61) amount of primary metal that is acquired by the industry2) amount of metal for manufacturing auto catalytic converters3) PGM recovered from the used auto catalytic convertersTable 3. Average values of Pt, Pd and Rh prices in theyears 2001 - 2008 9Year Price / $/kgPd Pt Rh2001 19,69 17,13 51,542002 10,91 17,42 26,952003 6,52 22,31 17,052004 7,47 27,27 31,502005 6,53 28,90 66,022006 10,36 36,76 146,442007 11,46 42,03 199,242008* 14,39 61,47 272,03* - average value from 4 months (01 – 04)Table 4. Pt, Pd and Rh recovery from the used autocatalytic converters 7Year Recovery / MgE J A OPlatinum2001 2,18 1,71 11,51 1,092003 3,58 1,87 13,06 1,552005 5,29 1,09 15,71 1,872007 6,69 1,09 17,88 1,87Palladium2001 0,93 1,24 6,22 0,312003 2,18 1,24 8,40 0,932005 5,13 0,93 12,13 1,242007 9,18 1,09 17,42 1,71E – Europe, J – Japan, A – North America, O – othersTable 5. Plants working for Umicore AutocatalystRecycling 4Name of plant PlaceUmicore Precious Metals Refining N.V. HobokenUmicore AG&Co KG HanauUmicore Brazil Ltd Sao PauloCycleon SASU ParisUmicore Autocatalyst Recycling Belgium NV HobokenUmicore Autocatalyst Recycling GmbH AlzenauUmicore Autocatalyst Recycling USA CovingtonFigure 3. Main steps in PGM recovery from the used catal-ytic converters 10aqueous solution of chlorate, perchloric acid, Cl2, H2O2,bromate, nitrate, and aqua regia. As a result PGM aremostly in the form of chloro-complex (MCl62-). The ob-tained solution contains PGM, but their concentration islow. So the next stage is to concentrate the solution andextract them from this solution. However, in hydro-metallurgical methods liquid wastes can be created inlarge numbers. This wastes might be very dangerous tothe natural environment. Figure 4 presents the exampleof hydrometallurgical method.In pyrometallurgical methods broken-up carrierscovered by the PGM are melted with the addition ofother metal which has a special function - to be a liquidmatrix. PGM pass into the alloy, while carriers are sepa-rated and scrapped. Obtained metal is rich in PGM, sothe next stage is the PGM purification 11,12.Both methods are very effective. Using them it ispossible to recover 95 % of platinum and 70 % of rho-dium. These two methods can be combined. As a resultthe high level of PGM recovery can be obtained 11.SUMMARYThe main requirements that the industry has to meetnowadays are the following: the environmental protec-tion, limiting the amount of wastes, reusing the second-ary material. So to protect natural environment againstharmful polluting gases catalytic converters are in-stalled in cars. Life time of these converters is limited.Thus the recycling of end-of-life catalytic converters iscrucial in order to economise on valuable resources andto minimise the environmental pollution connected withPGM production. Processing 2 Mg of the used auto cata-lytic converters can avoid mining 150 kg of ores and allthe following stages which are necessary to obtain puremetal.Today it is estimated that almost 30 % of all PGMever mined have been used for auto catalytic convertersand more than 2 000 Mg of these is still globally “on theroad”. So taking into account the prices of Pt, Pd and Rhit is profitable to recover these metals from catalyticconverters. Commonly hydrometallurgical methods areused in this recovery. However they also give some dan-gerous by-products.Taking into consideration the cost of the used autocatalytic converters and the cost of available technolo-gies it seems appropriate not only to export catalyticconverters but to start recycling them in Poland.REFERENCES:1 www.ipa-news.net2 www.sfa-oxford.com/environment.html3 www.davisconverters.com/catalyticconstruction.shtml4 www.autocatalyst-recycling.umicore.com5 Emission Sub System – Catalytic Converter, Toyota MotorSales, USA.6 Chevalier P.: PGM, Canadian Minerals Yearbook, 2004. p.41.1 – 41.16.7 Platinum 2007, Interim Review, Johnson Matthey, UK,2007, p.1-32.8 C. Hagelüken: Markets for the catalyst metals platinum, pal-ladium and rhodium, Metall, 1-2, (2006), p. 31-42.9 www.platinum.matthey.com10 C. Hagelüken: Precious metals process catalysts – materialflows and recycling, Supplement to Chamica Oggi/Che-mistry Today, 2(24), (2006).11 J.S. Yoo: Metal recovery and rejuvenation of metal-loadedspent catalyst, Catalyst Today 44, (1998), 27-46.12 Y. Kayanuma, T. Okabe, M. Maeda: Metal Vapour Treat-ment for Enhancing the Dissolution of Platinum Group Me-tals from Automotive Catalyst Strap, Metallurgical and Ma-terial Transactions, 35B, (2004), 817-824.Note: The responsible translator for English language are the Authors.136 METALURGIJA 48 (2009) 2, 133-136A. FORNALCZYK et al.: REMOVAL OF PLATINUM GROUP METALS FROM THE USED AUTO CATALYTIC CONVERTERTable 6. Some processes of PGM recovery from theauto catalytic converters 11,12Process SpecificationCN extractionHydrometallurgy,US Bureau of MiningSegregation N.E. ChemCatAqua regia HydrometallurgyChlorination Tanaka KikinzokuMelting method-1 PyrometallurgyROSETM method Pyrometallurgy, Nippon PGMMetal Vapour Treatment Pyrometallurgy, MatsudaSangyo LtdFigure 4. Scheme of hydrometallargical method 11

Izdvajanje metala iz grupe platina iz korištenih automobilskih katalitičkih convertera

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