2) United States Patent Mauldin (54) METAL RECOVERY (75) Inventor: Charles H. Mauldin, Fredericksburg, TX (US) ExxonMobil Research and Engineering Company. Annandale, NJ ws) (73) Assignee: (4) Notice: Suibjectto any disclaimer, the term of this pateat is extended of adjusted under 35 USC. 154(b) by 388 days. (21) Appl. Nos 12/922,792 Feh.6, (22) Filed 009 (65) Prior Publication Data $ 2009)0228325 A1 Sep. 10, 2000 Related US. Application Data (60) Provisional application No. 61/068,540, filed on Mar. 7.208, Gb Ince. BOL 38/60 (2006.01) BRE 904 (2008.01) cL 751383; 75/370; 75/744; $0227 G8) Field of Classification Search See application file for complete search history. None (66) References Cited US. PATENT DOCUMENTS 3578395 A S1971 Klokedab et ‘US008057572B2 (10) Patent No. 4s) Date of Patent: No US 8,057,572 B2 7.15, 2011 SASSARS A 1297 Deroest ta 936.000 B2* "82005 Mover Mukesh etal as 62003 ‘ilisoa sal POREIGN PATENT DOCUMENTS DE 102008061984 AL_72007 ED Osee07 AL L195 Re Denio ‘Toe WO WO20070%S AL_92007 (OTHER PUBLICATIONS ‘Kut R Rhoads, cal," Metal Recovery and Catalyst Rese fom the Photocatalytic Oxidation “of Copper Ethsenediamintetracetic Aci, Journal of Entronmentl Enpneering. Ap 204, pp. 425 V.¥, Kochehov, “Recovery of anmmonium pertenste during peo ceaing of plaiounechenien aly” devestpaVpahith UetmytsZavedeny, Gornyt ral 197, U2, pp 241-288 (barac Oni) M.A. Milusbeva, ota, “Extriton of molybdenum and shes From solutions of nite aisle acid leaching of molbenite concunles", Kompleinoe Isp sovaiie Mineral ogo Sire, 1986, 11, pp 585 Aburact Only. * cited by examiner Primary Examiner — George Wysromiceski on ABSTRACT A method is provided for recovering enim fom titania: supported, rbenium-contaning extalyst by treating the cata Jyst inthe reduced form with an acid in an amount andl fora time sufficient to dissolve the rhenium without dissing the suppor. 19 Claims, No DrawingsUS 8,057,572 B2 1 METAL RECOVERY Non Provisional Application based on US. Ser No. (61/068,540 filed Mar. 7.2008. FIELD OF THE INVENTION The present invention relates tothe recovery of catalytic metals on a solid titania support and in particular to the recovery of rhenium from titania supported Fischer-Tropsch catalyst BACKGROUND OF THE INVENTION Catalysts comprising a catalytically ative metal on asup- port such as silica or alumina are known in the at for hydro- nation reaetions. For example, catalyst compesing pli hum and rhenium supported on alumi has bee foun to be highly effective forthe reforming of naphtha, Similaey, a ‘catalyst comprising cobalt and enim tpportedon alia ‘or silica has been found to be elective forthe preparation of hydrocarbons from synthesis gas via the Fischer-Tropsch process, Although sheaium is an expensive metal, its excel- Jeat catalyst promoting activity justifies its eommercal use. In eeriin chemical reactions, iis believed wo be advanta ous to deposit a catalytic metal or metals om a titania sup- ort For example, cobalt and chenium supported on titania is preferred by some workers for Fischer-Tropsch resetions bocanse it mote active for CO conversion than when sup- ported on alumina or silica. Also, titania supported eatalysts may be prefered for use in hydrothermal environments ‘where alimina supports may show a tendency to degrade to ‘As swell knowa, during use catalysts tend vo become less ‘active and requite periodic regeneration, Regeneration typi cally restores the activity ofthe catalyst toa level approxi ‘mating is original condition; however, afer many rexenera- tions, the catalyst wll no longer be capable of being restored to a satislactory activity level. lt then becomes necessary £0 replace the deactivated or spent catalyst with fresh catalyst. [Noble estalytic metals are expensive, and hen, the tis replete with methods for recovering them from deactivated ‘catalysts containing them. For example, platinum ean be Fecovered from alumina supported platinum-containing cata- Iysts by dissolving the support with strong acidic or strong basic Solutions. Similarly, rhenium can be recovered from lumina supported shenium-containing catalyst by digestion ‘of the support with an acid or base followed by filtration to isolate the thenium-contsining catalytic metal. Thisapproseh is ot feasible with itania-supported catalysts because titania js not completely soluble in acid or base An object of the present invention isto provide a method forthe recovery of thenitm from titania-sapported catalysts and especialy the recovery of cobalt and rhenium from tae fis-supported cobslt and rhenium catalysts, SUMMARY OF THE INVENTION Accordingly, the present iavention provides & method for recovering thenium from a titania-supported enium-con- ‘aining catalyst, such as a rhenium-promoted cobalt catalyst, the method comprising treating the catalyst in the reduced form with an acid in an amount and for atime sutfcient 10 dissolve the chenium without dissolving the support. Tn one embodimeat ofthe invetion, cabalt and rhenium metals are recovered froma itania-supported cobalt and rhe- romoted metal catalyst by treating the catalyst i is 0 o 2 reduced form with an acid in an amon and fora time sui cient (o dissolve the catalytic metals and thereafter separating the dissolved metals from the undissolved suppor. ‘Other embodiments ofthe invention will come apparent from the description whieh follows, DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to eaalysts containing sheniumn supported on a titania catalyst suppor. Such rhe- nium-containing catalyst is used broadly herein (0 inelude rhenium and also shenium combined with other catalytic metals such as Group VII noble metals, for example, pat ‘num, palladium, shodium, osmium, iridium and ruthenium: and non-ble metals, such 2s, cobalt, nickel, and ion. The present invention is particularly applicable to ttania- supported cobalt and rheaium eatalysts such as those used in the Fischer-Tropsch hydrocarbon syathesis process. There- ‘ore, for eonvenienes the present invention wll be desribed by specific reference io titania-supported cobalt and henna catalysts, AS a proctical matter, the catalyst treated according tothe invention normally will hea used catalyst that has become at Teast partially speat or deactivate, However, rhenium can be recovered from fresh catalyst as well by the process of the invention In the method of the present invention, it is necessary that rhenium, aux other catalytic metals when present, on the ‘itana-supported catalyst be in the reduced state prior to ‘restment gecording to the invention, Ifthe rhenium and any other metals reno inthe reduced state, they ean he converted {o the reduced state by contacting the rhenium-containing catalyst with a redvcing stmosphere, for example, a kydeo- sen-containing atmosphere, ata temperature and pressure, fan fora time slicent to covert the rhenium to he reduced state. For example, a slury of spent, sbenium-containing, titania-supported catalyst in liquid hydrocarbons, such as ‘those priced in Fischer-Tropsch hydrocarbon synthesis process, is separated from the hydrocarbons in a catalyst separation zone, The separate catalyst then is contacted with fytirgen or a mixture of hydrogen and an inert gas at tem peratures in the range of about 250" C. to about S50" C., preferably from about 275° C. tosbout 425° C., and pressures ‘anging from above ambient to about 40 aum for time suf- ficient to reduce the eheninm. Typically about 30 minutes to bout 24 outs is sufficient to reduce the enum, “Altematively, a slury of spent, chenium-containing nia-supported catalyst in the liquid hydrocarbons may be rede i the presence ofthe liquid hydrocarhons by con: ‘aeting the slury with Hand CO in the molar ratio of abe 15to40atpressuresof | to about 10atm and preferably 10 1025 atm at temperatures of 175® C.t0450"C-and preferably 175°C. to 300? C. fora ine sulficient wo reduce the rheaium, ‘Then the rediaced catalysts separated from the liquid hydro carbons for treatment according to the invention, "The titana-supported catalyst comprising enum inthe seduced state, nd optionally, cobalt,also in the reduced tate js teated with sufficient acid to dissolvethe rhenium, andalso the cobalt if present, inthe catalyst In general, the aed sed ‘ill bea strong acd, suchas, sulfuric acid, hydrochloric acid, ‘agua regia and nitric acid. Preferably, the aeid used will be nitric acid “The amount of acidic solution used will be sufficient 1 at Jeast cover th catalyst and preferably will comprise a volume greater than the volume ofthe catalyst, for example, about 1 fo about 100 times the volume of the catalyst heing treated. The amount of acid preset in the solution must be greaterUS 8,057,572 B2 3 than the amount required to react and dissolve the metals present on the catalyst. In the ease of Fischer-Tropsch eata- Iysts there is much moze cobalt on the catalyst, on a mole basis, than rhenium, so the minimum amount of acl required ‘may he estimated to be atleast ro moles of acid per mole af ‘cobalt. An excess amount of acids preferred to ensuite rap, ‘complete dissoltion ofthe metals). More preferably, nitric disused and the molarity ofthe nitric aid may range fom, about 0.1 to 15M, preferably from about 0.5 to 2M, most preferably from about 0.7510 IM. Optionally, the catalyst may be ueated successively with the acid. “The treating ofthe catalyst may be performed at tempera tures in the range of ambient to the boiling point of the acid solution, depending on acid concentration. Optionally, during treating of the catalyst, the solution may bbe purged with airat any suitable flow rate, soch as from about 50 about 200 cc/min and, typically. about 100 ce/min, ‘heacid solution containing rhenium andoptionaly cobalt js readily separated from the titania suppor by filiraion. ‘Thereafter, the resulting metal solution may be processed in ‘onder to make it suitable for use in catalyst preparation orto Scparate and recover the dissolved metals. For example, the solution may be concentrated by evaporation or distillation aioe omston utes Aferexnsionof ‘and used directly inthe preparation of titania supported she nium catalysts or cobalt and renin catalysts. Optionally, the solution may be spray dred in order to recover the rhe= nium salt ora misture of eobalt and rein salts when eobalt js present. ‘Should separation and recovery ofthe cobalt and rhenium be desired, the solution may be subjected 10 electrolysis 10 plate oot rienium, for example, thereby separating trom the cobalious ions. Optionally, the solution may be passed through an appropriate ion exchangeresin i elTet separation ‘of the cobalt and shenium, The cobalious eomponcat may also be precipitated, with ammonium earbonate ora base like sodium hydroxide, and removed by filtration to provide @ predominately thenium-rich soluion, Rhenium oxide may alsa be recovered by high temperatare wasting of the cabal rhenium oxide mixture obtained by drying the solution. Te method ofthe invention is illustrated by reference to the following example. EXAMPLE, Aseries of runs were conducted in whieh a ram portion ‘ofa rutile titania-supported cobalt and rhenium-containing ‘catalyst was treated with one of three solvents listed in the following Table, The catalyst was prepared as follows, A shuny of 34.4 pans (by weight) of fumed TiO, 88 pars ‘alumina chlorhydrol sol (containing 23.5 wt % A1,0,), 0.6 pars silica sol (35 wt § SiO.) and $6.2 pans water was spray ‘ried ata rate of about 13 Ibfininute through a 9-inch wheel 0 o 4 ‘atomizer spinning at 10.000 spm, The spray drying chamber ‘was operated at inet sir temperature of about 285° Cand ‘an outlet temperatre of about 120° C. The spay died sup- port was calcined ina rotary ealciner at 1010° C. Thesuppart ‘was impregnated with an aqueous solution of cobalt nitate fand perthenic acid and calcined in air at 454° C. A socond ‘impregnation and calcination was applied to preduce a final catalyst containing 10.58% Co anil 1.20% Re. A portion of {his catalyst was reduced in hydrogen at 375°C, 1 atm, for | hour. For metals recovery tests, the reduced catalyst was ‘transferred into the rvating solution under argon, Tn one set of runs, the catalyst was in the reduced state in ‘cordance with the methos! ofthe invention. Ina compara tive set of runs, the catalyst was inthe oxidized state The S-gram portion of catalyst was added to SO ml of solvent and allowed (0 stand, with a continuous purge of ‘owing rand occasional swielng, For 30 minutes. The mix- ture war filtered, and the filtrate wa increased to 500 ml volume with de-ionized wate. The recovered catalyst was ried in a vac oven and analyzed for residual cobalt and thenium by X-ray fluorescence. The diluted filtrate was ana- Iyzed for cobalt and hen by inductively coupled plasma mission spectroscopy analysis. The results are shown in the Table below: TABLE Miubcnatiee Meuimehon Tea 1 ho, mas ke 2 IMiNO, nae mB 3 IMNuGH i097 a2 4 ko. nee 6 IMNKOR —Wwst 101 42 As canbe seen, Run 5, the example of this invention, isthe ‘only treatment resulting in appreciable metal extraction. This treatment ofthe reduced form ofthe catalyst with acid pro- duced a recovered solid with undetectable residual cobalt and low thenium, The extracted metals were present inthe dilated filtrate toa much greater extent compared tothe other treat- ‘ments, ‘What is claimed is 1. A method for recovering rhenium from a titan ported rhenium-containing catalyst comprising: ‘treating te catalyst, comprising thenitm in an unoxidized form, with an acid in an amount and fora ime sufficient to dissolve the rhenium without dissolving the suppor. 2. The method of claim 1 including separating the di solved rhenium from the suppor. ‘3. The method of claim 2 wherein the acids selected fom the group consisting of sulfur acid, hydrochloric acid, aqua regia, and nti acid, ‘4 The method of claim 3 wherein the acid has a concen- ‘raion sulicent 1 dissolve te rhenium, '. The method of claim 4 including purging the acid with air during the treating stp, 6. Themethod of elaim 4or§ wherein the acids nitrieacie 7. The method of claim 6 wherein the nitric acid has a molarity in the range of about 0.1 to about 15, 8. A method of recovering cobalt and theaium from a titania-supported cobalt and shenium-containing catalyst, the method comprising: supUS 8,057,572 B2 5 ‘weating the catalyst, comprising chenium in an unoxidized State, with an acid in an amount and fora time sulfcieat to dissolve cobalt and shenium without dissolving tta- nig; and thereafter separating the dissolved cobalt nd rhenium from the sup= ort 9. The method of claim 8 wherein the acids selected rom the group consisting of sulfuric cid, hydrochloric eid, aqua regia and nitric aid, having a molarity sulicient to dissolve the cobalt and rhenium, wherein the acid is used in anamount sulficent to a least eover the catalyst 10, The method of claim 9 wherein the acid is iti acid, 11. The method of elaim 10 wherein the nitric acid has & ‘molarity in the range of about 0.1 to about 15. 12. The method of elaim 11 incuding the step of process- ing the dissolved cobalt and chenium t© make it suitable for use in eatalyst preparation 13. The method of claim 11 including processing the dis- solved cobalt and rhenium to separate them. 14, The method of claim 13 wherein suid processing com- prises one of subjecting the solution to electrolysis to effect Separation and subjecting the solution 10 ion exchange t0 effect separation 15, A method for recovering rhenium from a titania-sup- ported rheniun-containing catalyst in which the rhenium iia ‘an oxidized sate, the method comprising reducing the catalyst to put the rhenium in the reduced state; treating the catalyst with rhenium in the reduced state with ‘anacid in an amount and fora time sufficient wo dissolve the shenium without dissolving the titania; and separating the dissolved chenium from the titania 16. A method for recovering rhenium frm a spent, supported, rhenium-containing catalyst slurred in liquid hydrocarbons, the method comprising: 6 ‘ontating the slrtied catalyst witha reducing gas com= Pising Hand CO in the molar rates of shout 1.5 to 4.0, fla pressure of fom 1 to 100 atm and a temperature of 175! C. to 450°C. fora time sufficient to reduce the henium inthe catalyst, separating the reduced etalyst fom the liquid hydro ons; treating the separited catalyst with an acid selected from sulfuric acid, hydrochloric acid, aqua regia and nitric ‘cid in an amount aa fora time sulicient to dissolve the ‘heaium without dissolving the titans and separating the dissolved chenium from the Hana, 17. The method of claim 16 wherein the acid is ivi acid having a molarity of about 0.1 wo about 15, 18, A method for recovering rhenium from a spent, titania- supported chenium-promoted cobalt catalyst sluried in lig- il hydrocarbons, the method comprising; ‘separating the catalyst from te liquid hydrocarbons in 3 separation zone; ccontecting the separated catalyst with @ reducing gas selected from hydrogen and a mixture of hydrogen and an inert gas, a temperature in the range of about 250° (C-toabout 350°C. and at pressure fm about ambient to about 40 atm for a tine sufficient to convert the thenium to the reduced state; ‘wvating the reduced rhenium With an acid selected fro sulfuric acid, hydrochloric acid, aqua regia and nitric ‘cid in an amount and fora ime suliient to dissolvethe ‘cobalt and shenium without dissolving the titania; and separating the dissolved cobalt and rhenium fom the tt 19, The method of claim 18 wherein the acid is nitric acid faving a molarity of about 0.1 to about 15