June 28, 1966 J. H. B, GEORGE 3,258,307 PROCESS FOR SEPARATING CADMIUM AND ZINC FROM MIXTURES THEREOP FEED CONTAINING SALTS OF Zn AND Cd IN AQUEOUS SOLUTION 2.9. Zn 80g AND Cd SOq Fited Nay 20, 1963 EXTRACTION wit AQ-INSOL. Liguio quaTerNary| AMMONIUM Zn SALT e.g Zn 804 FREE OF Cd IONS ‘QUATERNARY LOADED WiTH cd Tons, POSSIBLY CONTAINING TRACES OF Za IONS HALIDE STRIPPED LiauiD QUATERNARY AMMONIUM HALIDE STRIPPING Nig SALT €.9.(NHg)2 S04 PLUS Zn IN SOLUTION INVENTOR mes H, 8. Geors AgedUnited States Patent Office 3,258,307 Patented June 28, 1966 1 3,258,307, PROCESS FOR SEPARATING CADMIUM AND ZINC FROM MIXTURES THEREOF James H, B. George, Cambridge, Mass, assignor to "Arthur D. Little, lac, Cambridge, Mass, corporation ‘of Massacistts Tiled May 20, 1963, Ser, No, 281,653 10 Clalns. (Ch 236) ‘This invention relates to a process for separating ‘cadmium and zine from mixtores of compounds thereof ‘Cadmium is ordinarily found in nature 28 a, minor ‘consent of zine ores. These ores are usualy subjected to 2 smelting operation for the recovery of zinc. The ‘cadmium is deposited in the fumes from the Cottrell Precipitators; these fumes are calsined and then treated With sulfurie acid to dissolve the cadmium and zine as Watersoluble sulfates. Any lead prosent is also con- ‘verted to the sulfate, but as this is virtually insoluble in water it can be separated fom tbe soluble sulfates. ‘The later ate then commonly treated with zine dust 0 recover the cadmium as cadmium metal. This gives products of uncertain purity, as the separation is never To0s.with respect to either the zinc or the cadmium. With the increasing demand for these metals in pure form, uncontaminated with each other, a simple process {or their separation is of particlar interest ‘Objects of this Invention are accordingly to separate cadmium end zine values from mixtures of compounds thereof; to do so ina manner sch that substantially 100% separation is attainable; to employ an extractant ‘which ean be readily stripped and recycled; and to carry ‘ut the process in a simple and straight-forward manner ‘without fequlring unusual apparatus or conditions of oper- tion or the consumption of expensive reactants or teat- jing agents. Other objets will appear as this description proceeds "Tho process of this invention will now be described in defail, in connection with the accompanying drawing, ‘whit is in the form of a Now sheet illustrating a typical procedure or sequence of steps; without however intend- {ng to limit the iavention other than as set forth in the sccompanying claims, ‘The mixture of cadmium and zinc compounds to be treated in accordance with this invention is in the form ‘of a water solution of cadmium and zine salts. Although ‘any water-soluble 2ine and cadmium salts may be treated by the process of this invention, those commonly en= countered in practi are the sulfates, alone or mixed with the chlorides. Furthermore, the procedure of this inven- tion gives amore selective separation of the zinc and cadmium fons when they are fed as sulfates. While any proportions of one metal to the other may be bandied by the instant process, itis noted that the usual commerciat mixtures rum between about 1% and 10 grams per liter 6 of CA and about 20 to 50 grams per liter of Zn "The water solution of zine and cadmium salts is then subjected to an extraction slop, preferably in several stages, with a water-insoluble. quaternary ammonium hhalide in liquid phase. This quaternary ammoninm halide is ordinarily itself a liquid, but if # solid, it most be dissolved ia an organic solvent. Even If the quaternary is normally a liquid, it may be sufficiently thick that the Bddition of an organic solvent therefor is desirable or necessary for effective handling in the process of this Invention. The cadmium compounds thereby all pase into the water-insoluble quaternary phase, while neatly all the sine compounds remain in the aqueous phase, and are thus removed from the system free of cadmium ions. ‘The quaternary phase is then stripped by contacting with fn agucons solution of an alkaline compound eapable of Dreciptating cadmium as an insoluble salt thereof, pref- 10 6 2 26 0 6 0 45 0 0 6s 2 erably ammonium carbonate, in excess, whereby the cadmium is preciplated, eg, as carbonate, and the ‘ammonium is converted td sulfate or other salt, depending fon the natire of the feed, Ammoniam carbonate is the preferred precipitant, and in fact is necessary if any zine fons are present in the quaternary efllent to be stripped And ifthe cadmium is to be precipitated free of zine. The precipitated cadmium salt i removed by any con- venient means such as filtering of decantation, ‘The re- ‘maining liquid is in two phases, the quaternary and the aqueous. ‘The aqueous phase contains the ammonium Jons, as sulfate ifthe feed contained the eadmiom and ine'as sulfates, any residual zine from the inital extrac- tion, and the excess of the ammonitm carbonate of other alkaline precipitant. This phase may be processed for recovery of values therein, by conventional methods, if esirable.. The quaternary phase therefore has been ‘ripped of the cadmium and other compounds dissolved jn or mixed with it and can consequently be returned to the extraction step for reuse. "The zine values recovered in the aqueous moiety of the extraction sep are the same as those in the original feed, and may be separated from the wator and reacted ‘or otherwise treated or used in known fashion. ‘The precipitated cadmium compound may be washed and otherwise treated, and reacted or used, likewise in aovin fashion. ‘The quaternary ammonivm halide is a water-insoluble liquid, and may be represented by the formula RANX, wherein X is halogen, specifically chlorine, bromine, of iodine. Todine is the best of the halogens for effecting Separaiion, and bromine is nex, although all are opera: five in this process. They may also be present as @ mixture of two or al three, depending upon the effective: ness of seperation desired or the thoroughness “of Since the quatemary ammonium halide used herein is employed in the form of a liquid phase, it can be readily passed through the process as liquid ia intimate contact With the other liquids in the process, thus facilitating thor- ough contact of all the reactants, "No special provisions as fo temperature or pH are required; the quaternary i ‘operable at eny pH likely tobe encountered inthe process, ‘However, asthe quaternary is usually either a rather thick and viscous liquid, or may even be'a solid of a semi-solid, it i preferably thinned with a waterimmiscible organi solvent therefor, eg, xylene or toluene, t0 make it more easily handled in the process. Saitable examples of the quatemary compounds used herein are those wherein RJN— is treapryl methy! am- ‘onium, or distearyl dimethyl ammonium. ‘The R's may be “alike or different, and they comprise at least 19 hydrocarbon groups of at least 8 catbon atoms each, ‘They may faclude aryl or cycloalkyl groups. The total number of carbon atoms in the Ry radical is atleast 18. ‘The extraction step is conveniently carried ont in sores of countercursent extractions, tke number of which and the ratio of equeous to organie phases are not critical except that they should obviously be such a5 10 effect the desired separation, The same is true ofthe stripping step. ‘As a specific example, however, starting with an aque- fous feed containing about 5 g/liter Cd and 40 g/liter Zn, both as sulfates, extraction is carried out in six stages with a quaternary ammonium odide of the (ype herein described, in 0.5 N solution ia xylene. ‘The ratio of ‘agucous to organic phases inthe exlractions ie about 3:1, Zine sulfate free of cadmium passes out with tho final ‘aqueous phase; the final organic phase Is mixture of the cadmium sulfate and the quaternary ammonium fdide and/or reaction products thereof (Ihe exact com position not being material for an understanding of the8,298,807 3 present invention). A small amount of zine compound may also be present "Ammonium carbonate in waler solution is contacted with this organic phase. “The molar concentration of ‘ammonium carbonate in the water is not critical, but for ‘convenient operation 1 N to 3. Nis useful. The amount used in proportion to the organie phase should obviously ‘be such that all the cadmium is precipitated as carbonate, snd it is best to have an excess of the ammonium carbon ate to assure complete precipitation. “The quaternary emerges from the stripping step in is original form, ie, in xylene solution, and is thus ready for reuse ia the extraction step. Consequently, there is no loss of, the quaternary compound, other than trivisl mounts which may pass out withthe Cadmium carbonate ‘oF the ine sulfate. ‘Three components accordingly emerge from the strip ping steps solid cadmium carsonate precipitate, quater- ‘nary ammonium jodide in xylene, and an aqueots phe. ‘The latter contains ammonium suite, excess amimoniam carbonate, and any zine which had reached the stripping operation. The ammonium sulfate is of course produced by reaction between the ammonim carbonate and tho cadmium sulfate-quateraary ammonium iodide composi- tion. ‘Telaim: 1. A process for the removal of cadmium fons from aqueous’ solution of cadmium and zine sulfates which comprises: (@) repeatedly extracting said solution with an organi solution of a quaternary ammonium halide, (b) said solutions being immiscible with each other, (@) said quaternary ammonium balids having the Tormula RANX whereia X is-2 halogen selected from the group consisting of chlorine, bromine and lodine ‘and Ry is hydrocarbon radical containing at least 18 carbon atoms and contains at least (Wo hydro= carbon groups having at least 8 carbon atoms each, (@) continuing said extracting until substantially all ‘of said cadmium fons are in the organic phase and Substantially all of said zine ions are in the aqueous phase, (e) separating the orgunte phase and the aqueous phase, (E) stripping said organic phase by contecting the same with an aqueous solution of ammonium car bonate, until substantially all of said cadmium ions are precipitated as cadmium carbonate, and (2) separating out said cadmium carbonate. 2. A process in accordance with claim X wherein the ‘mixture resulting from said stripping step is sepa ws 20 20 10 4s 60 4 rated into its two phases, and the organie phase 1s re- turned for reeyeling inthe extraction step. 3. A process in accordance with claim 1 wherein said Jiquid quaternary ammonium halide is in solution in sylene. ‘4A process im accordance with claim 1. wherein R(NX is tricapryl methyl ammontum halide. 'S. A process in accordance with claim 1 wherein RANX is disteary! dimethyl ammonium halide. 6. A process in accordance with claim 1 wherein X is iodine. T. A process for separation of cadmium and zinc fons rom aqueous solution of soluble salts of cadmium and inc, which comprises (@) extracting said sofution with an organic. Tguid (quaternary ammonium halide immiscible with said ‘olution, (b) said ‘quaternary ammonium halide having the formula RANX wherein X is selected from the group consisting of bromine and fodine and the total nun- ber of carbon atoms ia Ry is at least 18, (©) separating the resulting two-phase liquid into tts ‘phases, the aqueous phase containing the zine ions find the organie phase containing the cadmium ions, (4) stripping said organic phase by contacting it with liquid medium which effects precipitation of the ‘cadmivin ions as an insoluble cadmium compound, (e) separating out sald precipitated cadmiom com: ‘pound, and (@) returning the stripped quaternary ammonium halide tothe aforesaid extraction step. 8. A process in accordance with claim 7 wherein sid liquid quaternary ammonium halide contains at least two hydrocarbon groups of at least 8 carbon atoms each, '9./A process in accordance with claim 7 wherein said liquid stripping medium comprises an alkaline compound which effects precipitation of said insoluble cadmium ‘compound. 20. A process in accordance with claim 9 wherein suid alkaline compound is ammonium carbonate. References Cited by the Examiner UNITED STATES PATENTS 10/1930. Stevens ota 3/1963 Preuss — 1,778,987 3,082,062 OSCAR R, VERTIZ, Primary Examiner BENJAMIN HENKIN, Examiner G.T, OZAKI, Assistant Examiner