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    Platinum recovery

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    Platinum recovery

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    9 views14 pages

    PT US Thomas1

    Uploaded by

    Moreno Marcati
    Platinum recovery

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    of 14
    (2) United States Patent Thomas et al. 1193517381 (10) Patent No. 4s) Date of Patent: US 7,935,173 BI May 3, 2011 oa 03) ow wo ep @y Gh (2) Gs) 66) PROCESS FOR RECOVERY OF PRECIOUS, METALS, Inveatorst Joseph L. Thomas, Yorba Linda, CA, (US); Gerald F. Brem, Chino Hills, ws) Assignee: Metals Recovery Technology Inc Analisi, CA (US) Notice: Subject to any disclaimer, the team ofthis, patent is extended or adjusted under 35 USC. 1S4(b) by O days. 127842,925 Jul. 23, 2010 Appl. No. Filed Int.Cl. Caan iss rR 346 (2006.01) US.C1. ocsnesnnennnnnn TSITAK: A222: 423/42 Field of Classification Search s/7a1 ‘2522, 42 See application file for complete search history. (2006.01) References Cited US. PATENT DOCUMENTS 92072 A 121975. ama tal + ‘91196. Maccitegor 31977 sleet a 1077 Aalst a MIST? Mackay eta SI9T% Baty S078. Hamngton 11079 Balnat S981 Sips2 1086 Liss 21990 S091 Dh Miv92 iu a an Der uy el Behnnm ot Ku Commis eal ‘xmierson el 5159.75 A 81992 Nakan stat Eussc03 A 101992 su Saouais A ‘31994 Lappect al (Coutinved) FOREIGN PATENT DOCUMENTS. iP 019567 AL 41982. (Continved) (OTHER PUBLICATIONS ls eta. The Adbosption of Povios Metals and Base Metals ona Quatemary Ammonium Group lon Exckange Resin. Minerals Eng cering ol 13, No.4, pp 401-414, 2000, (Continved) Primary Examiner — George Wysromierski Assistant Examiner —Tima M MeGuitey-Banks (74) Attorney, Agent, o Firm —Connally Bove Lodge & Huw LLP on ABSTRACT A hiydrometallurgcal process for the recovery of metals selected Irom the group consisting of platinam, palladium, rhodium, ruthenium, iridium, and gold (PM) from solids includes dissolving the PM and base metals nan ace halide ‘aqueous solution and precipitating dhe PM using substituted quatemary ammonium salts (SQAS). PM having multiple oxidation states may be oxidized or reduced to separate ‘through differential solubility. AU-SQAS is separated. by washing the precipitate witha suitable organic solvent, Rh SQAS and other PM with multiple oxidation states are di solved ina strong halide aed solution and oxidized to sepa- rte soluble Rh, Pband Pd are separated by boiling the initial acidic halide aqueous solution of metals in an excess of SQAS. The Phan Pl filtrate is oxidized and then Pd-SQAS js dissolved in aqueous ammonia and separated from insoluble Pb. shiny ofl SQAS and PL-SQAS are separated ‘through dissolution of leSQAS with NaNO, 20.Claims, 4 Drawing Sheets O# i ft ad US 7,935,173 BI Page 2 USS. PATENT DOCUMENTS S83.937 A 11/1998 Ker Gawsie 102000 Live al 6407298 BL '6 2002. Matsumoto ea ‘sm7304 BL 63003 Lidell 6890486 B2 $2005 Singh etal. TPssI8 Singh 7189380 Singh 7assaas lee. 20080190274 AL 102003 Singh 20080200839 AL 102003 Jenkins a. doovor007s2 AL 102004 Singh 20080060997 | Musa ea soowoneine Musa ta 200010263496 AL 102009 Rijn a. POREIGN PATENT DOCUMENTS re 0183200 A? 6\1986 » OUSiET AD Si1991 “i608 St1a “ua? aun aun aun 35351 ayn asa 2049 210633 dines 424600 i ‘oovorse BL 52003 » cae76s4 A 10/194 Wo — wo2msorstos AL 42008 OTHER PUBLICATIONS (Chen etal. An Effective Hy trothenmal Route forthe Synthesis of Multiple PDDA-Proectat Noble-Metal Nanstnuctres nor. (Chom. 2007, 46, 10587-10993 Desnoyes eal Saling-n by Quaternary Ammonium Salts, Cans- ian ural of Chee, vol 8 (1968) ‘Ghezz etal: Removal an recovery of aad un fons fom water ‘sing miceliarenancedulafiiation with ealionc surscan Colloids and Surfaces A: Physicochem. Eng Aspects 329 2008) 0, Sings eal. Catalytic behavior of nickel nanoparticis stabilized by Joweralkylammonium bromide aqusous medi. Applied Catal) ‘MPA! General 323 (2007) 5187, * cited by examiner US 7,935,173 BL Sheet 1 of 4 May 3, 2011 U.S, Patent aL 64 1614 wb 6t4 Ga) vorpal lira code -g—| —— mend ‘Aionoooy ig PUB MY WROWES. [oad if | ul | fonshe|[9|,_ rrr 9eineoue9 Nel vopevedes eu 1 30¥LS weiBeiq Bulsseold yy ejdwexg WL 64 US 7,935,173 BL Sheet 2 of 4 May 3, 2011 U.S, Patent wre,6eiq Buissesoig y eldwexg gL ‘Bl 7 fan an | Coa) : a 5 iG \ ' a[tou} Liatal | tt ee | —Lalfigl—( aoe <») — a ‘Suanovey Pa 1A BOWLS (a) ape) [i 2 SH) ‘Avenosey Uy tM IOVLS US 7,935,173 BL Sheet 3 of 4 May 3, 2011 U.S, Patent z 64 : v0 az ‘Bid (ay wore «- [hg] «| OS, « [ aE ve ‘Bly \ / ~ woase(. («) (n) lan ue! ag ower, ho, (r+ a iS soe a BS onal PEM Aisn070y Wy NIOVIS Pa 3) 6 \ a Avenooeu my TSOWIS v5] 4 B09 uaovs Pool «Tonal eH uiesBelg Bulsseooig @ aiduiexg Wz “614 ‘ogevedas enw +] 20VLS US 7,935,173 BL Sheet 4 of 4 May 3, 2011 U.S, Patent @ wesbelq Bulssecold g e|dwexy gz ‘Bi4 [ excray [aera] cr (seepage di [ne SS [ avoor ee <4) ee | ang (a) « [eosanpenle [ang T svose] ‘Auox0304 PUP d “A BOVIS ‘Oe mona taag( \ A SvOSI_y goyis «| SYOS!) pone S¥OSid) svosties sv0s) S¥vOS!I [ron] <+ al+—|odle— | 10H NO | af | Some a eH | enessia) | syosid vcs : _Svosty _| Sal ye ‘Menoo9y Pd pure Ny ‘A BOWLS US 7,935,173 BI 1 PROCESS FOR RECOVERY OF PRECIOUS. METALS BACKGROUND OF THE INVENTION “The fc ofthe preset invention is processes for the sepa ration of elements ‘Recovery, separation and purification of valuable precious metas, eg, pltinam [Pr palladium [Pl civ [, rhodium [RBi, ruthenium [Ru and gold [Au are typically tedious processes requiring repeated application of pyromet- allurzcal ydrometallugical or elecrowinning processes (0 ‘achieve acceptable metal recovery and metal purity. Most Source materials such as ores, spent catalysts, plating so tions, suclges, ore concentrates and smelter matte ate chemi cally complex, not oaly because ofthe diversity of previous metal elements but also because of the presence of lange ‘quantities of non-precious metals in the source material Recovery, purification and separation of precious metal ele- ments from these source materials are very dificul, time ‘consuming. expensive, and unsatisfactory with respect 10 some elements, particulary odin, ‘Previous metal chemistry is exceedingly complex and not “always well understood. In acidic halogen media, more spe «ifically chloride media, precious metals donot form simple ‘aqated cations of the type formes by common ase meals (ea., Nil"). Precious metals form coexisting eoortins tion complexes with wide variery of ligands, Tor example Known rhodium (l}) complexes include (RHC) [Ris (HO}F [RHCLCH,O}a} and [RACITT.O),} In IMchlo- ride solution, at equilibrium assemblage comprises about 80% [RACL (HOI, 10% [RhCIgI*, 10%. (RHC, (H0),)- and less than about 1% [RHCI,(,0),] See Grant A. 1989, The Separation Chesnstry of Rhodium and ee «dium, in Manzick ed, Precious Metals Recovery and Retin: ing, Proceedings ofthe Intemational Precious Metals In tute, p. However, the distribution of coexisting ‘complexes is unlikely 10 be an eaulibrim assemblage, par- ticularly in industrial applications involving multiple pre- ‘ous metals. The kineties oF igand exehange ates for pre- ‘iotlsmetalsexhiitexteme ranges. Forexample, the relative ‘exchange rate fo platinum (IV) is 10" relativeto paladin ‘Whereas palladium could undergo ligand exchange within hours or days, platinum (IV) ligand exchange may take ‘months. ICs likly that combined complex previous metal spoviation, reaction Kineties and other factors have neces tated development of present-day complex, tedious and time- onstming precious metal reovery profocols that often su fer from disappointing outcomes or expense ‘Current industry practice for precious metal recovery relies hicly on solventextraction thatistypically supplemented by Jon exchange and traditional chemical processes in spite oF icienies, long processing time, lange volumes of soli- tions anda myrid of other problems. US. Pat. Nos. 8,201, 942 and 7,294,202 review some ofthe difficulties related to precious metal recovery and purification. Precious metal covery and puifieation processes in these patents as Well as US. Pat. No. 7.175.818 disclose tedious and complex pro- ‘esses that donot fully solve current imitations or high costs, The precious metal industry has exerted great effort over the past decades in developing and improving upon solvent ‘extraction processes for gold and some platinum group met- als. Inspiteof substantial progress, protocols ypicalytlize diffrent extractants foreach element. Solvent exchange pro= ‘esses are equilibrium controlled. Fach solvent extraction may require multiple contacts ofextactantand mother liquid stripping of the extractant, sevubbing of the extractant to 0 o 2 remove impurities and reneration ofthe extractant, There ore, complete extraction of the desired metal may not be ‘achieved and cumulative metal loss can increase with each extraction. In addition, contaminating elements may also be extracted along with the desired metal, thus requiring purfi- cation of the desired metal. Solvent extractions, while the method of choice, may be complicated further by poor sol- vent-mother liguid separation, solubility of the extractant in the mother of serub solutions, multiple side streams of the sired metal large volumes of aqueous solutions requiring ‘reatment a5 Well as toxicity or fammability ofthe organic Tonexchange processes have been selectively incorporated into industrial previous metal recovery protocols bul are of ‘more limited we than solvent extraction processes and do not solve recovery and refining challenges. lon exchange pro- ‘esses are typically equilibrium controlled and may not com- pletely remove the desired metal. Jon exchange processes may also suffer from poor selectivity for precious metals ‘which result eo-extraction of other precious metals o¢ from ‘oextraction of contaminants. Typically, ion exchange resins {or precious metals are expensive, hve relatively low capsac- ity thus requiring large volumes, require large volumes of rip soluions to recover the desired metal and extracted ‘metals often require additonal purification ‘Other chemical provesses of precipitation and volaliza ‘ion may be used in conjunction with solvent extraction and or ion exchange. Typically, these processes are used 10 remove selected elements from the mother liquid orto purify sta ofinslicient purity. ‘Separation and recovery of rhodium is particularly vex> ing problem. In typical curent extraction processes, hodinm romins atthe end alter recovery of other platinum group ‘cals, This hs at least Uhroe disadvantages: rhodun is lost in the many sidestreams of upstream extractions, rhodium is Tocked up during recovery of other precious metals, and rhodium an ifidium are often ia the final solution and sepa- ration ofthese two metals is dificult hy any known method. In spite of much elfon, rhodium recovery and refining remain a vexing problem, There are no known readily usable solvent extractants fr thodum. U.S. Pat, No. 5,201,942 pro- posed solvent extrciat for rhodium requiring complexing ff Rhwith a high molar excess of in, The proposed solvent extraction process has distinct limitations: it presumes fsmisim snd iridium have been removed by shodium extraction s ot quantitative and Rh a processed to remove tin which may be in 2 10 times molar excess, fon exchange processes for Rh recovery and purfc ‘ion on an industrial seale have likewise retuned disappoint- ing results or have been unsuecessl. By necessity the indus- try largely utilizes tedious precipitation and dissolution methods 0 purify rhodium, "Tosmeet the demand for precious metals, the industry i in ‘need ofa simpler, lower cost altematve to current practices that is capable of recovering precious metals fom chemically verse primary and secondary sources. ‘All the U.S. Patent references described above are incor: porated by reference in their entirety fr all useful purposes. ‘SUMMARY OF THE INVENTION ‘The present invention is directed to a hydrometallurgiel process forthe recovery of precious metals selected from the ‘up consisting of platinum [P¥) palladium (Pa, thoiam {Rh}, ruthenium [Ru iridium fr} and gold [Au] from base ‘tals in an acidic aqueous halide solution. In the process, substituted quaternary ammonium salts are employed to pre US 7,935,173 BI 3

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