@ mm (00639.9140(94)00246-0 (Conjrah +1998 EhaverScence Lid Prntedia Gen Briain A nos seid AN ION-EXCHANGE METHOD FOR SELECTIVE SEPARATION OF PALLADIUM, PLATINUM AND RHODIUM FROM SOLUTIONS OBTAINED BY LEACHING AUTOMOTIVE CATALYTIC CONVERTERS RoMutes Gatra* and Sancon J. AL-Bazst Department of Chemistry Northesstem Minois Univesity, Chicago, IL 60025, US.A. (Received 17 May 1984. Revised 18 August (994, Accepted 16 Aust 1994) ‘Summary—An ion-exchange method has been developed for the separation of palladium, platinum and "hodium fom solution thats highly acidic and contains considerable amount of le, lumi, ion and cerium, obtained by leaching a used honeycomb type automotive catalytic converter. A. column of ‘Amberlte IRA-98 anion-exchange resin was found appropriate to recover platinum metal Foes the pregnant solution. Selective stripping of these metals from the resin was achieved by eluting rhodium fist with 60M hydrochloric ac, then palladium with 2 1% ammonia solution at ambient temperature, and Platinum with S% ofthe reagent at elevated temperatures. Optimum conditions for leaching these metals from the catalyst were SOM hydrochloric acid snd 04M sodium chorate at 70°C. Ths method cam be applied to both analytical as well s large Scale operations. It is simple, economical, and relatively safe for human exposure and the environment There are two common automotive catalytic converter catalysts in use.' The so-called “low- loading’ form contains about 370 ppm of plati- num and about 160 ppm of palladium, and the “high-loading’ form contains approximately 60% more of each of these elements. There is also an ‘extra high-loading’ catalyst which con- tains about 850 ppm of platinum and 350 ppm of palladium and even some varieties which contain more palladium than platinum. These palladium-platinum catalysts are usually re- ferred to as two-way’ catalysts since they cause the oxidation of both carbon monoxide and hydrocarbons. Rhodium has been introduced into catalytic converters. Since then. approximately 73% of the world production of rhodium is consumed in the production of autocatalysts.? These monolithic automotive catalysts are typically Cordierite type honeycombs with platinum, pal- ladium and rhodium, These catalysts are called ‘three-way’ catalysts, since they not only oxidize carbon monoxide and hydrocarbons but also various nitrous oxides. “Present address: AlliedSignal Revearch & Technology, Des Plaines, IL 60017, US.A. ‘Author to whom correspondence should be addressed The average loading of platinum group metals per catalytic converter has been 0.05 troy ounces of platinum, 0.02 troy ounces of palla- dium and 0.005 troy ounces of rhodium.’ Each year, approximately 10 million automobiles are scrapped in the United States. Based on an equivalent number of converters, itis estimated that $00,000 troy ounces of platinum and 200,000 troy ounces of palladium and 50,000 troy ounces of rhodium will be wasted annually just in the United States, The annual world Consumption of these metals for autocatalyst use could double or triple the above numbers. Since these metals are in limited supply, a successful process for their recovery from cata- lytic converters will play an important part in their future availability and prices. Dissolution of palladium, platinum and thodium presents special problems owing to their generally high ionization potential (the first ionization potential of Pd=83 eV, Pt=90eV and Rh = 7.5eV). This coupled with the complex variety of elements in the used catalytic converter makes it difficult to leach these metals from the catalyst, and to isolate them from the pregnant solution, Furthermore, the increasing variety of catalysts produced, the apprehension over industrial pollution, and 299290 concern with human exposure to chemicals is making the development of new processes to recover these metals from the catalysts more dificult. ‘The method commonly employed for a selec- tive separation of palladium, platinum and shodium from the solution obtained by leaching catalytic converters is based on ‘wet chemical procedures.'* Platinum is precipitated as am- monitum hexachloroplatinate(IV) and rhodium as ammonium hexachlororhodate(II1) by satu- rating the decomposed mother liquor with am- monium chloride. Palladium is precipitated as ammonium hexachloropalladate(IV) after oxi- dation to palladium(IV). This method is con- sidered inefficient by today’s standards in terms of the degree of separation achieved, the yields obtained, and the complexity of the operation. Solvent extraction methods” have ben devel- ‘oped to overcome the problems related to tra ditional practice. However, this technique is characterized by very slow kineties* and selec- tive back-extraction does not appear to be easily achieved." Furthermore, the utilized organic solvents tend to be volatile, flammable and toxic which may introduce pollution to the environ- ment. The purpose of this study was to develop an ion-exchange method for the selective separ- ation of palladium, platinum and rhodium from the solution obtained by leaching them from the honeycomb type catalytic converter. The opti- mum conditions for leaching these metals from the catalyst were also investigated EXPERIMENTAL, Reagents Anion-exchange resins Amberlite IRA-68 (20-30 mesh particle size) and Amberlite IRA- 93 (20-30 mesh particle size) both from Alfa Products, and Amberlite IRA-400 (16-50 mesh Particle size) of Aldrich Chemical Company, were used in their chloride forms. These resins were equilibrated with 10% hydrochloric acid before use. Palladium, platinum and rhodium stock solutions of 1000 ppm were prepared by dissolving a weighed amount of palladium(I1) chloride (Aldrich Chemical Company), platinu- m(I1) chloride (Johnson Matthey) and thodi (ITT) chloride (Aldrich Chemical Company) 10% hydrochloric acid solution. A stock sol- tution of 10.0M lithium chloride and 045M lanthanum nitrate hexahydrate (Li/La) was pre- R. Garand S.J, AL-BA2 pared in deionized water. All other reagents ‘were of analytical grade. A used honeycomb type automotive catalytic converter ground to minus 60 mesh particle size was obtained from Catalytic Converter Refining Co., Northlake, TL, Apparatus A glass chromatographic column (18 cm long and 4.8 mm inner diameter) was used. Palla- dium, platinum and rhodium were determined with a Spectraspan IV (Beckman Instruments) direct coupled plasma atomic emission spec- trometer. The flow rate was controlled by an Econo peristaltic pump (Bio-Rad, California) ‘An ATC autosampler (Techni Lab, NJ) was used to collect 2 m! fractions. Leaching procedure ‘The schematic diagram for leaching palla dium, platinum and rhodium from the catalytic converter is shown in Fig. 1. A 20.0 g sample in 2 250 ml beaker was treated with 95.0 ml of the desired concentration of hydrochloric acid. With continued stirring, the heterogeneous mix- ture was heated (see discussion for details) and then a small amount of sodium chlorate was added slowly from a 50.0 ml buret. After cool- ing to room temperature in an ice bath, the solution was filtered into a 100 ml volumetric flask and distilled water added to the mark. This ‘Automotive Catalyst = [Pecan] Lo Fig I, Flow diagram for leaching palladium, platinum and ‘thedium from automotive catalyst.Leaching sutomotive catalytic converters 251 solution was then divided into two 50.0 mi portions, To one portion, 2.50 ml of the LijLa solution was added to suppress interferences and improve detection limits. This portion was then used for the analysis of palladium, plati- ‘num and thodium. The other portion was used to determine the acidic content. Recovery and stripping procedure Batch ion-exchange procedure. Resin (1.0 g) and 10.0 ml solution of palladium, platinum and rhodium were stirred moderately for 2.5 hr at room temperature in a 25 ml beaker. After ‘equilibration the solution was filtered through a Whatman # 2 filter paper. The loaded resin was then washed for 5 min with 10.0 ml deionized water, filtered and mixed with 10.0 ml of the stripping solution for 1.5 hr at room tempera- ture, To the filtrate from the recovery and stripping experiments, 0.50 ml of the LijLa solution was added and the filtrate solution then analyzed for palladium, platinum and rhodium. Column ion-exchange procedure. The column was filled with a slurry of the resin until the settled resin bed reached the top of the column (20 g of dry resin). A 25.0 ml portion of the pregnant solution was passed through the column at a flow rate of 1 ml/min controlled by the peristaltic pump. The platinum metals were then selectively eluted from the column with the stripping solution, In both studies, 2 ml frac- tions of the eluate were collected with auto sampler, treated with 0.10 ml of the Li/La solution, and analyzed for palladium, platinum and rhodium, RESULTS AND DISCUSSION The optimum conditions for leaching palla- dium, platinum and rhodium from the used catalytic converter were established by invest gating the effects of various parameters. Effect of sodium chlorate concentration Varying the concentration of sodium chlorate from zero to 1.1M (Fig, 2) indicating that at zero sodium chlorate, less than 5.0 ppm of palladium, 0.5 ppm of platinum and 1.1 ppm of thodium were recovered. Leaching increased sharply with increasing sodium chlorate to a maximum of 32.5 ppm palladium, 290 ppm platinum and 7.0 ppm rhodium at 0.4M sodium chlorate and then decreased slowly. The effect of sodium chlorate on the concentration of hydro- sem (Pena ee Fig 2, Effect of sodium chlorate concentration on leaching palladium, platinum und chodium: autocaalyst Weight =200 "g. [HCl.q==48M, temperature = 70°C heating period = 1 fre () Pa (2) Pt (C) Rh. chloric acid of the leached solution was linear; acid concentration decreased with increasing sodium chlorate (fits the least-squares equation [ACT = — 1.878 [NaClO hou + 3.624). The decrease in acid concentration may explain the decrease in palladium, platinum and rhodium leached beyond 0.4M sodium chlorate concen- tration, Effect of hydrochloric acid concentration Leaching palladium, platinum and rhodium from 0.4M sodium chlorate solutions increased from 2,0 ppm at zero concentration to a maxi mum of 31.4 ppm at L.8Af hydrochloric acid (Fig. 3). The amount of platinum leached in- creased sharply from 0.8 ppm at zero concen= tration to 327 ppm at 7.2M and then remained constant at higher concentrations of acid. About 0.1. ppm thodium was leached in the absence of hydrochloric acid and 5.5 ppm at 18M which further increased to a maximum of 8.1 ppm from a S.4M solution. The increase in the amount of palladium, platinum and rhodium leached with increasing acid concen- ation may be related to the formation of chlorocomplexes of these metals [PECK PIC and RhCK,~] which are much more stable than their aquocomplexes [Pd(H.O};". PU(H,O)$" and Rh(H,O),"ast Prem [Pa a Fp Mott Fig. 3, Effect of hydrochloric acid concentration om leaching palladium, platinum and rhodium: autocatalyt weight =200 g, [NaClO,]~04M, temperature — 70°C, heating petiod = I hr (O) Pd (A) Pt, () Rb Effect of temperature Palladium leaching was independent of the temperature (Fig. 4), while platinum leaching increased from 176 ppm at room temperature to 0 » _ - _ _ i £ ea 5 « i 2 Teoma 20 Fig. 4. Temperature effect on leaching palladium, platinum and shodium: autocatulyst weight = 200g. [HCl 48M, [NaCIO,]= 0444, heating period = Thr: (0) Pa (a) PLD) Rh, R, Gata and S.J, At-Bazs a maximum of 325 ppm at 95°C. Rhodium leaching increased from 3.3. ppm at room temperature to a maximum of 9.5 ppm at 95°C. The effect of temperature on the hydrochloric acid content of the leached solutions showed a linear decrease in acid concentration with tem- perature which can be expressed by the follow- ing regression equation [HCI]. = —0.043 1+ 5.108 over the temperature range of 32° to 95°C studied. Because hydrochloric acid evaporates at elevated temperatures, a tempera- ture of 70°C was recommended for optimal leaching, Separation of palladium, platinum and rhodium Evaluation of anion-exchange resins. Three anion-exchange resins, Amberlite IRA-400, Amberlite IRA-93 and Amberlite IRA-68 were tested using a batch procedure to select a resin that is efficient in both recovery and stripping of palladium, platinum and rhodium, Recovery of these metals from a 40M hydrochloric acid solution containing synthetic mixture of 25 ppm of each metal, and stripping with 5% NHy solution were investigated. Although the quanti- tative recovery of palladium and platinum could be achieved with both Amberlite IRA-400 and Amberlite IRA-93 resins, the latter exhibited more favorable results in the recovery of rhodium and its stripping with platinum (Table 1. Recovery of Pa, PL and Rh. The recovery of palladium, platinum and rhodium from a preg- rant solution that was made 280 ppm platinum, 340 ppm palladium, 380 ppm rhodium and which contained 6450 ppm aluminum, 1610 ppm iron, 947 ppm cerium and 397 ppm lead showed a recovery of 99% palladium, 97% platinum and 61% rhodium (Table 2). The results also indicated that 13% aluminum, 32 iron, 18% cerium and 80% lead were retained by the resin, The decomposition of RhCI;- in Tablet. Recovery and stripping fiienies of palladium, platinum and rhodium using Amberite IRA-400. Amberlite TRA.93 and Amberite TRA-68 resins Te Recovery” Supping? RA Rh Pd Rh Cr re ee) 999 17st) Bos wo ‘volumes 10 mk resin weight 10 g iil concen of palladium = platinum = rhodium =20 pps, 4.04 hydrochloric acid 15% NH solution (8)Leaching automotive catalytic converters Table 2. Separation of palldium, platinum and rhodium from the pregnant solution by Amberlte IRA resin “Stripping Motal* _% Recovery 6M HCI 5% NH, solution 09 98 7 07 7 a % nd? Solution volume 25 inal concentrations of palladium 340 ppm, platinum 280 ppm and rhodium 380 ppm resin ‘weight 20 5 flow rate 1 mlimin ‘nd: Not detrrsined, aqueous solution to [RhCl,_.(H:0),]* types ‘may be the major problem in its recovery."” Elution of rhodium. In an attempt to strip thodium selectively, the resin was treated with 25.0 ml of 6.0 hydrochloric acid solution at 1 ‘ml/min at room temperature. Palladium and platinum remained on the resin whereas 80% of the rhodium was eluted (Table 2). Therefore, a complete elution of rhodium can be achieved by controlling the volume of hydrochloric acid, When the stripping solution was tested for aluminum, cerium, iron and lead, both alumi: num and cerium’ were quantitatively cluted while 84% of the lead and 44% of the iron were luted under these conditions. These two metals were removed completely with 25.0 ml deionized water at 1 mi/min. Elution of palladium. When the resin from previous investigation was treated with 25.0 ml of 5% NH, solution (flow rate { ml/min), 98% palladium was eluced with only 7% platinum (Table 2). Elution of palladium and platinum from the resin with different volumes of 5% NH, solution was studied by passing the eluent through the column loaded with these metals and treated with 25.0 ml each of 6.03 hydrochloric acid and deionized water (Fig. 5). A 40 ml of 5% NH, solution was sufficient to strip palladium com- pletely with only a small amount of contami- nating platinum. To inprove the selectivity of cluting palladium, different percentages of am- monia solution from I to 10% (25.0 ml volume) were studied. Less than 2% of ammonia sol- ution was sufficient co strip palladium selectively (Fig. 6). Furthermore, concentrations below the limits of analytical detection were obtained when the cluted solution was tested for iron, lead, aluminum and cerium. Elution of platinum, The stripping of small amounts of platinum from the resin (Figs 5. 6) say be related to the slow rate of formation of Pt(NH,);" in comparison to Pd(NH){* com- 23 (rane Fig. Elution curves for palladium and platinum: 5% NM, olution (9). lw rate | mimi (C1) PS. (O) Pt plex.!* In an attempt to improve the stripping efficiency for platinum, the effect of column temperature was studied. The column was packed with resin and loaded with platinum, then immersed completely in a water bath main- tained at 65°C. An aliquot of 25.0 ml solution of 5% NH, (heated to 65°C) was passed through at a flow rate of | ml/min. The percentage of platinum recovered increased from 7% at room ve HA 4 8 sau cen, Fig. 6 Bet of percentage of aqueous ammonia (is) on stripping plladium and platinum: solution volumes = 25.0 ol ow rate fmiin: (C1) Pa (2) PL2s temperature to 42% at 65°C, When this exper- iment was repeated at a flow rate of 0.5 ml/min, the per-cent of platinum eluted further im- proved to 65%. This indicates that a complete recovery of platinum from the resin can be accomplished by controlling the percentage of ammonia solution, its flow rate and the column temperature. Capacity of Amberlite 1RA-93 for Pd and Pt uptake The capacity of the resin to retain palladium and platinum was estimated from a. break- through study: 275 ml of 4.0M hydrochloric acid containing 350 ppm platinum and 275 ppm palladium were passed through the column (packed with 2.0 g of the resin) at a flow rate of ml/min. From the plot of concentration of the ‘metal unretained versus volume of the solution collected (Fig. 7), capacities of 0.44 mol plati- num/kg resin and 0.85 mol palladium/ke. resin were calculated. Owing to these high resin ca pacities, Amberlite IRA-93 may be of practical value in recovering palladium and platinum from a solution obtained by leaching these metals from automotive catalytic converters. Recommended process for macro scale recovery of Pd, Pt and Rh A recommended process for leaching palla- dium, platinum and rhodium from the automo- five catalytic converter and their selective recovery from the leached solution using Am- berlite IRA-93 is summarized in Fig. 8. A5.0M hydrochloric acid solution is mixed with the catalyst sample and then heated to 70°C. At this, R. Gata and S.J. AL-Bazt temperature, a 0.4M sodium chlorate solution is added slowly and the mixture is filtered. The pregnant solution is then passed through the resin, The column is washed with 6.0M hydro- chloric acid solution followed by deionized water. The hydrochloric acid solution (contain- ing non-saturating amount of rhodium) is saved for reuse. The resin is then treated at room temperature with 1% NH, solution to strip palladium followed by 5% of the reagent at elevated temperatures and a slow flow rate 10 lute platinum. The separation of palladium and platinum from the eluted solution could then be processed either by reduction to metal or pre- cipitation as (NH,),PdC1, and (NH,)sPtCl, by hydrochloric acid." The original leaching sol- ution is then adjusted to 5.0M hydrochloric acid, heated to 70°C and reused several times 10 Teach platinum metals from a new batch of the catalytic converters and passed through the resin again. After several recycling processes, the leaching solution becomes rich in rhodium. This recycled solution can then be passed through the resin many times to recover thodium. After each cycle, the resin is washed with the saved hydrochloric acid solution 10 strip rhodium which then can be recovered by a selective reduction to metal CONCLUSIONS The described ion-exchange method, using Amberlite IRA-93, for sclective separation of palladium, platinum and rhodium from acidic solutions obtained by leaching honeycomb type catalytic converter can be considered an efficient technique for the separation of these metals on i | z Fig. 7. Breakthrough curves for pulladi and platinum: [Pa] =275 ppm. (Pe 27S ml, flow rate mln: (6) Pa, (O) Pt solution volume 350 ppm. (CY) = 44Leaching automotive catalytic converters ——— L 28s ‘eacted Slson 0 | [ram Fig. 8 Simplified flow diagram for leaching, recovery and stripping process, ‘an analytical scale and could be applied to large scale operations. This method is not restricted solely to automotive catalysts but is also appli- cable to petrochemical catalysts, ores, and in- dustrial wastes. It is noteworthy that owing to the nontoxicity, nonvolatility, and nonf- ammability of the ion-exchange resin, this ‘method may present fewer environmental haz- ards than the currently adopted solvent extrac tion and precipitation techniques. Acknowledgements The authors would lke to thank Me Raymond Sloun from the Catalytic Converter Reining Co for providing a catalytic converter. The esarch was sup ported by a grant from the Northeastern Ilinis University Committee on Organized Research REFERENCES 1. M.E. Browning. G. 1 Edson and 1S. Bubes. The Thin! Conference on Precious Metal. p20, Minos, 1989. 2 L Manzick. Precious Metals Recovery and Refining. 7. Historical Publistion, Texas 190, 3 E:D. Zysk, Patinunr Group Metals Seminar 1985p. 9 ‘Washington DC. 1986 A.C. W. Ammen, Recvtery and Refining of Precious Metals, p.242. Van Nostrand Reinhold, New York, 1984, S.J.E, Barnes and J.D. Edwards, Chem, Ind 1982.5 Ist 6 RI, Edwards, Proc. tt. Solent Exte. Conf 2. 7. LR. Reavil and P, Charlesworth, Prot. tn, Sattent Eur. Conf. 1980, 3, 80, 8. S.J. Alas and A’ Chow, Talons, 1984 3, 815 9. $5. AbBadi and H. Freer Anal. Chim, det, 1991 as, 235 10 5.2. AkBaviand H. Freier org. Chom, 1989.28, 817. M1 S.J. AbBaai and H, Fret, Solvent itr lon Exch 1987, §, 268, 12, S.J AlBazi and H, Preiser, Sofrent Evin fon Esch 1986, 4, 1121 1. RLE-Connich and D.A. Fine. J. Aon Chem Soe a3 314 14 BV. S. Towson and M. Levin, JS. afr: Cher, la 1974, 2, 87 1S. G. Foo and M. E. Browning. Semoun or Reon Reclamation an! Rein of Precious Metals, pres tation no, 12. California, (981 1979.4, 1961,