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July 9,1946. J. R. XCIUNNINGHAM SEPARATION ' '. 2,403,640 COBLALTITE Filed April 15, 1942 PULP ’ ,1 r2 3v _ . _ . CHALCOPYRITE - *- ACID 5“. . /8 7—\ . I e ANGUE —<# 7 ' 9 f“ ' - 13 15 I6 PYRITE-PYRRHOTITE COBALTITE //v VE/VTOR - John R,.Cunn_|'nghc|m ' 5]..-" ?ick/warm" Patented July '9, 1946 2,403,640 UNITED STATES PATENT? ‘OFFICE I 2,403,640 SEPARATION OF COBALTITE John R. Cunningham, Larkspur, Calii’., assignor, by mesne assignmen Corporation, San Fr ts, to California Research ancisco, Calif., a corpora tion of Delaware Application April 15, 1942, Serial No. 439,068 1 ‘Claim. (Cl. 209—1.67) - 2 This invention relates to the separation of co ‘Other objects achieved by. this invention will be ' apparent from the following description and the baltite from minerals containing it. ' Cobaltite, a mineral of the approximate _com-' ‘ appended claim. position CoAs'S, is an available cobalt mineral , ‘ I have found that cobaltite can be readily and eiliciently‘separated i'rom pyrite or pyrrhotite,‘ or from both if present together, by subjecting the from which the pure'metal or its compounds can ‘,be economically produced, provided, however, the cobaltite can‘ be separated'in concentrated form mineral mixture to treatment with lime, and thereafter subjecting the mixture to ?otation in a system of pH not greater than about 7 in the pres from other minerals associated therewith. ‘Among - the minerals frequently associated with cobaltite are pyrite and pyrrhotite. Chalcopyrite is also 10 ence of a xanthate collector and a depressant for the cobaltite, and ?oating the pyrite and/or pyr Separationof minerals by ?otation methods » rhotite away from the cobaltite in this system of. has advanced to the point where almost any min controlled pH with the aid of the said ?otation eral or group ofminerals can be separated from ‘ ’ any other mineral or group of minerals of dis Without embarking upon any detailed scenti?c tinctly different ?oatability and ?otation char explanation of the phenomena involved, or in any acteristics. The di?iculty arises in separating ' ‘minerals of very similar ?oatability and ?otation _ ,way limiting the invention to a theory, I believe frequently found in association with cobaltite. agents. characteristics. . ' ' ' ' that the delicate separation of cobaltite from , In the instant case, cobaltite is found associ 20 pyrite and/0r pyrrhotite thus e?ected is due in large part to pre-liming the mineral mixture, ated with gangue (earthy matter of little or no which depresses the cobaltite more effectively and mineral value), pyrite and pyrrhotite and, fre more durably than it depresses the pyrite and quently, with chalcopyrite. The separation of the pyrrhotite, so that when the system‘ is subse group cobaltite-pyrite-pyrrhotite from both the‘ quently neutralized ‘or acidi?ed,‘ the cobaltite is gang‘ue and the chalcopyrite is easy and straight still depressed but the pyrite and pyrrhotite are forward. The gangue canbe'separated by ?oat not depressed orare not as fully depressed as the ing the minerals in an acid or neutral circuit, em- ; cobaltite. Upon ?otation treatment in a system ploying the usual ?otation agents for ?otation of of pH not greater than about 7 in the presence ; sul?de minerals, whereby the cobaltite-pyrite pyrrhotite are ?oated and the gangueis rejected. 30 of a xanthate collector (a known class of collectors suitable for use with sul?de minerals) and a depressant for the cobaltite (of which many well- ' Also, chalcopyrite can be readily separated by ?oating it in a basic circuit. _The' separation of known examples are available as hereinafter de scribed), the cobaltite is still, substantially non ever, a problem of wholly different magnitude. ?oatable but the pyrite and pyrrhotite are ?otable, The ?oatabilities and ?otation characteristics of 35 especially in the presence of an activator. these three minerals are so. similar that, hereto If the mineral mixture consists of cobaltite plus fore tomy knowledge, they have not been sep ' pyrite and/or pyrrhotite, and no more, only the arated except by cumbersome and expensive cobaltite. from the pyrite and pyrrhotite is, how single ?otation stepv described is necessary, and. this step may be repeated, subjectingthe cobaltite It is an object achieved by the present inven 40 reject and the pyrite-pyrrhotite ?oated mixture‘ tion toe?ect a‘ facile, economical separation. of each to a further similar ?otation treatment. cobaltite from ores, concentrates and the like‘ con ' However, if, as is usually the case, gangue is taining it in association’ with pyrite, pyrrhotite, methods. _ . . or other'iron sul?de minerals of similar ?otation characteristics. ‘ ' - . 45 It is a further ‘and particular object achieved by this invention to separate cobaltite. from ores, concentrates and the likevcontaining it in associ-' ation with pyrite or pyrrhotite, or vboth, together ' with chalcopyrite. so present, or if, as is often the case, chalcopyrite is present, in the mineral mixture, a preferred modi?cation is employed. A single illustration with respect ,toja chalcopyrite-gangue-cobaltite pyrite-pyrrhotite ore will su?ice‘ toillustr'atelthis _ 1 preferred modi?cation‘. In such case the ore, suitably ,vcomminuted, will ?rst be liined, as by mixing with lime water, mix mam 3 . l 8 long enough to clean and brighten the surface - ing dry lime with the ground ore and. adding of the sul?de particles. The. pulp, thus adjusted water, or otherwise making an alkaline pulp con as to pH. is withdrawn through va conduit 1 and introduced into a ?otation cell 8 where it is sub jected to ?otation in the presence of suitable quantities of a frother, such as pine oil, and a xanthate collector. such as amyl xanthate, ‘or pine‘oil as vfrothing agent and potassium ethyl potassium amyl xanthate, whereby all of the sul xanthate as collector. The reject of gangue, co ?de minerals, that is. pyrite, pyrrhotite and cobal baltite, pyrite and pyrrhotite, in pulp condition, tite. are ?oated and the gangue is rejected. The 10 is then rendered approximately neutral to acid . reject or tailings of gangue is withdrawn through " and the mixture'is subjected to ?otation in the a conduit 9 and suitably disposed of,‘ and the taining lime. The chalcopyrite is then ?oated. Any other mineral ?otable in a basic circuit may likewise be- ?oated. This ?otation step may be accomplished in the usual way, as by the use of presence of a xanthate collector to ?oat‘ the co ' baltite, pyrite and pyrrhotite away from the gangue. It will be noted that in this step the ?oated sul?des are withdrawn through a conduit the cobaltite depressant has not been used. The next step involves the use of a xanthate collector and a cobaltite depressant, whereby the cobaltite pressant for cobaltite, such as mono calcium aryi reference to a simple cobaltite-pyrite-pyrrhotite the pyrite and pyrrhotite are ?oated and the co l0 and introduced tola ?otation cell ll . Suitable quantities of a frother, such as ‘pine oil, a ' cobaltite is also ?oated. - This is possible because 15 xanthate collector, such as amyl xanthate, a de sulfonate, and an activator, which may be a heavy metal salt, such as ferric sulfate, along with suf is depressed and rejected and only the pyrite and ficient water to form a suitable pulp, are added pyrrhotite are ?oated, as described above with 20 and the mixture is subjected to ?otation. whereby mixture. ' ' baltite is rejected. If ‘need be, more acid may be ' _In the‘more complex separation of cobaltite added to adjust the pH _of the pulp to 7 or less. of the pH in this and the following chalcopyrite, gangue, pyrite and pyrrhotite, as 25 Maintenance ?otation step at 'l or less, preferably from 7 to 4, just described, the order of steps is highly impor is especially important because the difference in tant. It is important that the chalcopyrite be ?oatability. between cobaltite on the one‘ hand ?oated ?rst in a basic circuit and that gangue and pyrite and pyrrhotite on the other hand is be subsequently separated. I have found that if small. By means of careful control‘ of pH' and 30 the gangue is ?rst separated and the chalcopyrite proper selection of ?otation agents,- I am'able' suc from an o're containing it in association with or other like mineral is then separated, the ?o tation products and tailings in subsequent sep aration steps are contaminated with chalcopyrite. ' cessfully to ?oat the pyrite and pyrrhotite away from the cobaltite despite this small difference in ?oatability. The cobaltite reject or tailin‘gs is re 35 moved through a conduit l2 and the ?oated pyrite of steps as described above. and pyrrhotite are removed through a conduit l3 ‘ Of course, if chalcopyrite and gangue are sep and introduced into a ?otation cell It. Suitable arated by other means, or if a mineral mixture quantities of the same reagents as used in cell H, is_- available which does not contain chalcopyrite and of-water and/or acid if need be. are intro or gangue, the procedure of the invention may 40 duced into cell ll and the pyritd-pyrrhotite con- ' This difficulty is avoided by following the order be suitably modi?ed or simpli?ed. centrate is subjected therein to a second ?otation similar to that carried out in cell l I. thus produc ing a further quantity of cobaltite as reject or agrammatic drawing representing a process of tailings and ?oating a purer pyrite-'pyrrhotite separating cobaltite from an ore containing it in 45 concentrate. The latter concentrate is removed association with chalcopyrite, gangue, pyrite and through a conduit I5 and the recovered cobaltite pyrrhotite. ‘ ' is removed through a conduit _IB and joined with Referring to the single ?gure of the drawing. the ?rst portion of cobaltite concentrate removed The process of my invention will be more fully understood by reference to the accompanying di- - - an ore comprising chalcopyrite. pyrite, pyrrhotite. conduit 12. cobaltite and gangue, suitably ground and made 50 ‘ through In the preferred embodiment illustrated by the into a pulp (about 20-30% solids) and made alka-' drawing and described above, the’pyrite-pyrrho- ' line with lime solution.v is introduced through a ' tite-cobaltite concentrate resulting fromthe sep vconduit i into a ?otation cell 2 and is therein aration of game in ?otation cell 8 is subjected to subjected to ?otation in the presence of a froth 1a double ?otation as shown, but instead of this, ing'agent such as pine oil and :a collector such 55 _ a single ?otation step, or three or even more ?o as potassium ethyl xanthate. The frothing agent tation steps, may be employed. Thus the cobaltite and collector may be added separately to the ?o concentrate may be subjected to further ?ota tation cell, or maybe incorporated in the ore or ~~ tion to separate any residue of pyrite or pyrrhotite pulp before it is introduced into the ?otation cell. therein and the pyrite-pyrrhotite concentrate agent is added to the Preferably, the frothing 60 my likewise be subjected to further ?otation to‘ pulp in the ?otation cell. ' The ?otation step car-, ried out in cell 2, and subsequent ?otation steps hereinafter described, may be carried out in ac-_ cordance with standard procedure, such. for ex in f‘Principles ofMineral Dressing" by A. M._G'audin (McGraw-Hill), 1939 , ample,'as that described edition, pages 402-423. ‘ The chalcopyrlte is float - ' ed in cell 2 and is- removed through a conduit 3. The reject or-tailings. containing the cobaltite. along with pyrite, pyrrhotite and gangue, is withdrawn through a conduit 4 and introduced ' into a conditioning vessel 5 to which an acid. such, for example, as sulfuric acid or hydrochloric acid, is added through a conduit,‘ in quantity su?ieient recover any residue of cobaltite therein.‘ The lime used in pretreating the mineral mix ture. or- in the chalcopyrite separation‘ may be, pure or impure lime. For. example. it may be a dolomitic lime. The acid used in the neutraliz ing or acidifying steps is preferably sulfuric acid. but other acids capable of producing the’ desired pH. such ashydrochloric and phosphoric acids, I may. be used.‘ - Following are speci?c examples of suitable ' frothing. collecting, activating and 'depressing agents capable of use in accordance with my-v invention, these speci?c examples belonging to rdco811M classes of ?otation agents; many of 7 which set forth in Gmidin’s "Principles of ' 76 material is preferably held in conditioning vessel ‘ to adjust the pH of the pulp to about 4 to '1. The, asoaeso 6 Mineral Dressing,” referred to supra, at the pages’ indicated below: ' ' Frothing agents (page 363): ' LbJton of ore III. Reflotation of pyrite-pyrrhotite concentrate: Pine oil Frother, such as pine oil ______ -_' Higher alcohols Collector, preferably amyl xan thate __________________ __'___ Fuse] oil Cresylic acid 0.5 to 0.1 0.1 to 0.25 1 Depressant for cobaltite, such as . Eucalyptus oil Camphor mono calcium aryl sulfonate__ 0.25 to 0.5_ Activator, such as ferric sulfate-_ ’ 0.5 to 2 10 Collectors (page 371) : _The depressants used in accordance with my in Amyl xanthate Butyl xanthate Propyl xanthate , ‘ vention are of the type of non-?oating dispersing agents. Their function, as stated, is to depress the cobaltite. They accomplish this result by se - Ethyl xanthate ‘ ' Sodium and potassium salts of the above 15' lectively wetting the surface of the cobaltite particles, thereby inhibiting bubble attachment to xanthates and ?otation of the cobaltite particles. The acti Sulfonated petroleum sludge vators, which are preferably heavy metal salts, Activators (pages 395 and 396): have the effect‘ of promoting the'ac'tion of the Ferric sulfate ' '20 collecting agents. They appear to e?ect this re Lead, nitrate sult by preferential adsorption of the heavy metal Lead chloride ion, e. g. ferric ion, on the pyrite and pyrrhotite Copper sulfate particles, and forming heavy metal xanthate, e. 'g. Copper chloride . ' . ferric xan'thate. _ Cobaltite depressants (pages 393 and 394) : 25 : I claim: Mono calcium_aryl sulfonate Mono sodium aryl sulfonate . In a method‘ of e?'ecting separation of cobaltite' ‘ Sodium sul?de Sodium cyanide from a pulp mixture thereof with chalcopyrite. gangue', and from iron sul?de minerals of similar Sodium silicate ?oatability'to the cobaltite: that sequence of steps which consists in ?rst rendering the pulp mix ture alkaline with lime; adding av frother and a may vary considerably. However, in ?oating py .' collector comprising a xanthate, and subjecting rite, Pyrrhotitc and cobaltite away ‘ from the vsaid pulp to a‘ ?rst froth ?otation to ?oat said gangue, in ?oating‘ pyrite and pyrrhotite away chalcopyrite from said gangue, iron sul?de min from cobaltite, and in re?oating the pyrite 35 erals and said cobaltite; then adding. acid to ad pyrrhotite concentrate, I prefer to use the agents Just the pH of the reject of gangue, iron sul?de in the following approximate proportions: minerals and cobaltite to a value not greater than about 7 and a collector comprisinga xan , LbJtonof ore I Ll'lotation of pyrite,- pyrrhotite thate; then subjecting the pulp thusformed to a '40 second ‘froth ?otation to‘ ?oat the cobaltite and and cobaltite away from 881181-16! . iron sul?de minerals from the gangue; then add Brother», such as pine oil .-__~_____ 0.3 to 0.2 ing to the cobaltite and iron sul?de a depressant The amounts of such agents that may be used Xanthate collector,v preferably . amyl xanthate_.;..-__e ______ __ 0.25 to 0.75 . 45 II. Flotation of pyrite and pyrrho- tite‘ away from cobaltlte: Frother, such as pine oil______ -..' 0.5 to 0.1 erals comprising a' heavy metal salt; and subject ing the pulp thus formed to .a third froth ?ota tion to ?oat said iron sulfide minerals from said ‘Xanthate collector preferably cobaltlte in the presence‘of said depressant._ ' amyl xanthate_____-_____l__.._ 0.25 to 0.5 Depressant for cobaltite. such as , mono calcium aryl sufonate--- 0.25 to 0.5 Activator, such as ferric sulfate-.. ' for the cobaltite a collector comprising 9. mn thate, and an activator for the iron sul?de min 1 to 2 50' JOHN R. CUNNINGHAM.