United States Patent Faine et al. 6 NON-OCHEMICAL METHOD TO HEAP. LEACH COPPER CONCENTRATE! 3) Inventors: Jaime Rauld Fane, Santiago (CL); Freddy Aroca Alfaro, Santiago (CL); Raul Montealegre Jullian, Santiago (CL); Abra Santiago (CL) (73) Assignee: Minera Michi (2). Notice: Subject to any disclaimer the term of this pateat is extended or adjusted under 35 USCC. 1544b) by 0 days (21) Appl. No. 10715914 22) Filed: Nov. 18, 2003 (5) Prior Publication Data Us 2006014408 AL Jul, 29, 2008 (30) Foreign Application Priority Data Now 26,2002 (C1) 2e9-n02 (1) Ime cL (C228 3/08; C298 3/10 (2) US.Cl. T5712 8) Field of Search 75712 66) U.S. PATENT DOCUMENTS. Sas6915 A 21903 Pozo =] ¢ 1U$00692675382 692675. US 6,926,753 B2 Aug. 9, 2005 (10) Patent No. 5) Date of Patent sors A G6RISS A soe70 A 72000 ‘2003223927 AL * 122003 6196 S200 Pincheies Alvace ota Sharp etl Kot Rawle ast FOREIGN PATENT DOCUMENTS sso na ‘11 (OTHER PUBLICATIONS “Designing the Leach System for Ceara Negwo ore;” Kacz- marek, AF, et al; Cobre International Conferences Ele: Irofining and Hydrometallargy of Copper; vol 4, Oct. 10, 1990, pp. 437-152. Primary Examiner—Melvyn Andrews (74) Attorney, Agent, or Firm-—D. Peter Hochberg; Sean ‘Mellino; Katherine R. Vieyea on ABSTRACT A procedure t agglutinae ore concentrations which ean be ‘of copper, on a gravel heap, o be leached on a non-lloded bed which comprises: artificially adhering the concentrate 10 the surface ofa sold material base, which can bean artificial ‘material, ot a stony substance; the agglutinated material is stockpiled, forming a lesching pile; and is irigated with @ leaching solution containing atleast Cl, Cu, and Fe ions 17 Claims, 7 Drawing Sheets J (11) (10) | (13)U.S. Patent Aug, 9, 2005 Sheet 1 of 7 US 6,926,753 B2 @ | —@ (3) cw eS FIG-1U.S. Patent Aug, 9, 2005 Sheet 2 of 7 US 6,926,753 B2 [+ J (10) g (11) (13) FIG—2 tt (12)U.S. Patent Aug, 9, 2005 Sheet 3 of 7 US 6,926,753 B2U.S. Patent Aug, 9, 2005 Sheet 4 of 7 US 6,926,753 B2 100 - 90: 80: 70: Ht cot 1 404 Hit | T 1 RECOVERY (%) ° e 6 uw eS Be = we 4 3S & 30 aoe 20: I | LAT 10. TU SADUREOBBEuED 40 60) 60) 10077 20) TIME (DAYS) FIG—4(a)U.S. Patent Aug, 9, 2005 Sheet 5 of 7 US 6,926,753 B2 TIME (DAYS) 8g 2282922890890 9 06 oo 8 RF 6H FHA HS (%) AuaAooga FIG—4(b)U.S. Patent Aug, 9, 2005 Sheet 6 of 7 US 6,926,753 B2 =| 350 La | | 300 | | ‘© EXPERIMENTAL] 250 200 TIME (DAYS) 150 100 50 Ee (lion on oo a 100: 90+-- 804 70: 6 (%) ANaAOOga FIG—5(a)U.S. Patent Aug, 9, 2005 Sheet 7 of 7 US 6,926,753 B2 350 fol bate be -HE | + | T 200 TIME (DAYS) 100 t e ¢ 100° 390 (%) ANTAOOTa FIG-5(b)US 6,926,753 B2 1 NON-BIOCHEMICAL METHOD TO HEAP LEACH COPPER CONCENTRATES BACKGROUND OF THE INVENTION 1, Field of the Invention ‘The preset invention relates toa procedure to agglutinate ‘copper concentrates in gravel heap, tobe later leached on non-flooded bed, fo which an agelotinating solution con- taining calcium chloride, and a second solution conttining sulfate ion, are added, 2. Description of the Prior Art The copper concentrate, usually obisined by loation, can be currently processed in order to obtain metal coppet, by using bot. pyrometallurgical and bycrometaurgical tech- rigues. As indicated by its name, the pyrometallurgical techniques, by far the most common ones a present, eome- ‘spond to processes using high temperatures such as roasting, ‘smelting, conversion, and fire refining, 10 obtain metal ‘copper. On the other hand, the bydrometallurgical tech- niques correspond t0 those processes using aqueous solu tions for copper extraction. During the last decade, the inerest in using hydrometallurgcal processes to teat eoppet ‘concentrates bas significantly increased, asthe environmen talist pressure has increased on the pyrometallurgical processes, which have a serious impact on the envionment A number of processes, most of them patented, have been studied for hydrometallurgical treatment of the copper concentrates, 10 avoid them to be processed by the usual Pyromctalurgical techniques. From the industrial point of view and t this presentaton’s interest, all the processes for hydrometallurgicsl treatment ofthe eopper concentrates, can be divided ino two major felds: weactor leaching and heap leaching, being the first one where 4 high qumber of new proposed processes exist In spite of the high number of processes developed in reactors, none of them has become an alternative to the pyrometallurgieal process to treat the ‘copper concentrates. ‘On the other side, unlike the treatment of copper concen: leales in reactors, heap leaching has shown to be a very ‘Valuable technique to treat a great amount of copper ores, Copper ofe leaching, both for oxidized ores and some sulphide ores, is currently one of the essential pillars suse laining this metal production worldwide. The procedure as referred to by this invention, corre= ‘ponds to the use ofthe heap leaching method, as applied to ‘concentrate leaching rather than or ia addition to, copper ‘ores, At this point, it shouldbe stressed that copper concen trates are mainly composed of sulphide enpper species, with a much smaller component of oxidized species. [Next brief summary of the procedures as deseribed in papers and patents for reactor copper concentrate leaching Will be presented, as well asthe alms made to teat hese ‘concentrates in heaps, making use ofits higher advantages, both practical and economical First, for reactor copper eoncentrate leaching, a series of ‘chemical and biochemical reactions have been proposed, ‘which are either oxidizing or oxidation reaction catalysis, able 10 dissolve the sulphide species containing copper ‘Among these are, mainly: oxidation by means of ferric ion, ‘or through the ehlorine—copper ion, nitric oxides, eas chlorine, gas oxygen, and ferrooxidans bacteria, ‘Apart from the bacterial leaching processes, which are those closest to an industrial applicttion, the following processes are currently under development, even though % o 2 ‘pone of them shows the progress required for high tonnage industrial application: pressure leaching, bot leaching, nileo- catalyst leaching, and bromide-chloride leaching, Al these processes require the concentrate to be finely divided. OF all of them, thse of interest wo this discussion are the processes using the ferie ion, and the copper ion, in a Chloride environment, because use of the chloride im is the basis of the present invention ‘The use of chloride to help dissolve the copper concen= trates has been stdied, and patents have been generated for ‘over 100 years. Leaching sulfides by using chlorides such as FeCl, and CuCl, is currently recognized as one ofthe most elective methods to produce concentrated solutions, from Which copper i directly extracted, with the addtional advantage of obtaining silfur as an clementary substance, ‘Among the known and patented processes using reactors to leach the concentrates, ae the following: ‘The Canmet process, Minemet Recherche and Broken Hill process use sulfate-chloride solutions. ‘The solutions ‘oblained are treated by solvent extetction inthe texiional "The Cymet process uses # FeCl, and CuCl mixture as leaching media. The CuCl obisined is precipitated from the solution and reduced to metallic Cu by using a hydrogen Few in a Muidized bed reactor, a Duval Coxporation’s Clear process, copper chloride is used as leaching means along with brine conaining potas- sium and sodium. Iron s precipitated in second pressurized sage as potassium jarosite. Copper is clectolyzed in cuprous slate 10 obtain copper erystas into the cathode. Copper chloride is regenerated from the cuprous in the ned, and returned to leaching. ‘The USBM process is similar except forthe use of ferric chloride rather than copper chloride, and copper is dissolved as cuprous chloride. Copper is" directly produced by elecirolysis, ina diaphragm cell. Reagent is regenerated in te eell anodic compartment, The Dexlee process produces the anodic copper to dis: solve in the presence of oxidizers. This reaction takes place in diaphragm cell, The Cu sponge obtained as deposit in the cathode compariment contains all the impurities of the sarting material ‘he Elkem process is used to each complex Cu, Zn and Ph concentrates in a countercurvent fertie al copper chlo- ride solution, Cu is recovered, as » sponge, by EW. In = variation ofthis process, 2 CuCl, is produced, from which ‘copper is separated by SX before the EW stage, in which the {quality ofthe copper produced is improved. In this process, the Zine i extracted from the leaching solution by wsing ‘eibutilphosphate. The Pb is precipitated as PbCI.. The process is quite complicated, as problems exist related to the ‘SX cireult andthe shape ofthe metal obtained is oot suitable Tor direct sales without an additional treatment, The Cuprex process uses a NaCl and FeCl, based so tion to dissolve the copper sulfides, obtaining. a CuCl, solution. The Cu is extacted by using SX in chloride media, in thee countercurrent sages, Re-ekiraction is earried out by using pure water and producing a concentrated) CuCl; solution, Which i transferred to a diaphragm cell. The Ct produced is granular capper (Ihe commercial eathode) and the operation is rather complex. ‘The Intee process carries out leaching by using an on izing chloride solution containing bromide chloride (Halex). Once the solution has been purified by using lime, sranular Cu is extracted by electrolysis in an ion-selectiveUS 6,926,753 B2 7 membrane cel. The Cu as produced, even though of goad chemical quality, cannot be commercialized without a0 Additional kestment All these processes use vessels or reactors, generally agitated, and at a relatively high temperature, w obtain the ‘oxidizing and dissolving ceactions of the copper sulfides, ‘The reactors agitated have several disadvantages, which enerlly make the process fo be non-easible. Fist, mast of| the sulfides are esistant to leaching, or dificult ofeach, 0 they require very long reaction times and, consequently, ‘equipment is very big and expensive, Second, «high power supply is required t0 maintain the solids suspended and mixed. Abo, leaching in agitated tanks is carried out in aygressive environments by using concentrated reagents, fand often at very high temperatures. Phis makes the reactor to be very sophisticated and expensive, (On the other hand, and compared to the reactor treatment, there exists the heap Teaching treatment to process sulphide ‘ores, This procedure is clearly simpler and cheaper than that fof the reactors, since it docs not require. sophisticated ‘equipment, of high temperatures, or pressures highcr than the atmospheric one. The time frames involved, however, a longer than those involved in reactors. In spite of hi, the investment required is much smaller, since in this ease the reactor is the heap itself, the forming of which is muck ‘eheaper than tha of a reactor. Disregading the fact that heap leaching is widely used the industry, both for tating oxidized ores. and some sulphide ores, the stockpile concenrate leaching i just in its ‘experimental stage This, because a pile of pure concentrate, in ise, can n0t form a stable heap without a previous teatment. When you {ty odo tis, a numberof problems related tothe flow of the irrigating solution arses, such as canalization, water ‘stagnation, and poor drainage, allthis due tothe small size ‘of the particles of which it is composed. For this reason, alternate ways to maintain a concentrate heap tha is sroc- turally stable hive been studied ‘Various attempis to agglomerate the conccatrate particles to each other through the well known pelletizing process, by using water with or without an agglomerating agent are known, Initially, these pellets can be effectively Incated to form a stockpile. However, since most of the mineral ‘compounds forming the pellet react leaching, these ‘quickly loss tbe consistence and, eventually, the stockpile collapses. ‘Analternate procedure partially solving, o atleast dimin= ‘ishing the distdvantages already mentioned, consiss. of having the icles adhered 1 a base material This later al material, or a stony material, such as ore, discarded ore or rock, barren material, gravel, ‘le, crushed to the appropriate size ‘Some processes using this concept have been recently “developed. For example, U.S. Pat. No, 6,063,158 by Sharp ‘etal. year 2000, uscs « polyethylene sphere packing called “Bioballs", which have the advantage of having a large ‘external surface 1o which the concentrate particles can adhere. In this patent, the concentrate is mixed wit graphite fd a bacterial nultient before adhering to the sphere packing, thea the st is loaded on a heap and subjected 10 bacterial leaching, the same as if t was a mineral stockpile In this case, a polyethylene-melacrilate polymer is used 3s & binding agent (On the other hand, US. Pat. No. 6,083,730 by Kohr, year 2000, uses a similar concept to test sulfide concentrates al jnstead of using an artificial substatum as that in’ the % o 4 paragraph above, it uses a set of coarse particles, which may forrespond to washing, gravel, or olher rack. Once the ‘oncenteate particles have adbered to the particles forming the coarse substratum, a stockpile is built and the concen- trate bioleaching takes place. Here, the autor mentions the possibility of adding an adherent polymer, even though be ensues that this is not necessary when the eoncenteate is ‘wel, a6 a sluy. This sime author has a number of patents in the USA, covering this subject, however, they refer to gold ore or copper concentrate bacterial leaching, and in no fase 10 chemical leaching The idea of using an artifical or natural packing to obtain various hydrometalurgial rections is nol new. I began as 4 way to provide a base for bacterial growth through the Tormation of biofllm, which bas been proven even at an industrial level ‘Unlike al the above, the invention described below refers {fo a new process 0 adhere the concentrates 0 the coarse particles, followed by « non-bacteral process based only in chemical reations, the purpose of which is treating any copper concentrates by hydrometallurgical processing, as described below. SUMMARY OF THE INVENTION This invention refers to an exclusively chemical method, thats, non-biochemical, and also ina chloride eaviroament, to heap leach copper concentrates by taking advantage ofthe fact hat these conccateates canbe setifiilly adhered to the surface ofa mineral, barren material, discarded or, grave, Teach gravel or other sold material of similar characteristics ‘working as a base, commonly called: "gravel" Accotding to this invention, the concentrates are, in frst place, added 10 the solids base into a standard mixing ‘equipment, such an agglomeration drum or pelletizing disk, by making use of a reagent working a a binder or adhesive, ‘whose active principle is, essentially, the hydrated calcium sulfate or gypsum, oblsined "in situ” from the calcium chloride eaction slong with sulfurie sei. “The main characteristic ofthe mixture obtained with the concentrate plus the mineral, gravel or other material, as Geseribed above, plus the caleium chloride in aqueous solution and the alton a sulfurie acid, consists in that the ‘concentrate particles strongly adhere 1 the surface of the ‘mineral beetse the formation of gypsum, which is natural adhesive material formed by the teaetion of the calcium Chloride with he sulfuric aci, is added. The main advantage ofthe formation of such aggregate is thatthe heterogeneous ‘mixture as sich physical charicerstcs tht can be piled up Torming a heap, typical of those commonly used at the ceurent hydrometalungical plants. The concentrate is thus ‘Incorporated to the sfockpile, and it benefits from all the advantages of this technique in terms of economy and simplicity. Once this heap has been formed, the next step consists in irrigating it with a chloride, irom copper and other ions concentrated leaching solution, as well as some residual sulfate from the sulfuric acid added. The highest walence of ‘opper and iron chlorides (that i, +2 and +3, respectively) act 38 oxidizers othe copper sulphide ores, dissolving them 4nd transferring them 10 the itigtion solution as lowest valence of said chlorides (that is, +1 and +2, respectively) like reaction products, Once the Teaching solition, contain- ‘ng the eopper values, has lft the ile, the eopper content is partially extracted theough the tational solvent extraction Process and the solution already treated in this stage, sil ‘containing a significant proportion of the copper extracted,US 6,926,753 B2 5 is recycled to the heap in order to continue leaching more ‘copper sulphide species Copper that has been extracted in the solvent extraction stage is reextracted and eleetrowon or erystalized by means fof procedures that are currenlly widely known, 10 obtain, high purity copper cathodes, of the less interesting enppet salts, ‘This process can be also applied to any materials with physial characteristics’ similar to those af the concentrates, that i, inly divided, containing copper, uch as preci ‘or tailings ofthis metal BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the preferred way of adding a concentrate ‘orotber fine atrial fo the main flow of anore, or a dlfereat ‘stony material In this figure, the concentrate i added to the ‘main flow of ore by means of a belt, perpendicular tothe flow of mineral going tothe agglomeration drum. Later, the heaps ave irrigated in the standard way, and the solution 2 recovered is subjected to solvent extraction and electox~ inning process. FIG, 2 is a flow diageam corresponding to the preferred realization ofthis invention FIG. 3 shows the physical aspect of the material some time after the agglutination has occurred, The sizo ofthe agglutinated particles and the green color typical of the formation of eopper oxychloride can be seen FIG. 4is a graph showing the recoveries as obtained for both heaps, whic turned out to be of 93.7% in both eases FIG. ia graph showing the recovery curve obtained (a) for example (2) and (b) for example (3), where the final recoveries of 90.2% and 85.5%, respectively, can be appre- ‘ciated The evident inerease ofthe recovery’ atthe final par ‘of the curve i due to the washing elect already mentioned, DETAILED DESCRIPTION OF THE INVENTION In summary, the industrial application process to treat ‘copper concentrates through the procedure inthis invention, ‘consists in two consecutive and complementary sages. First, the copper concentrate adheres to the stony material base nto an adequate equipment, hereunder designated “azelu- tination” to distinguish it from the process commonly ealled “agglomeration”, whichis the process where the particles of the same materi adhere to each other. Next, the material formed is piled up ata pad, forming a leaching heap. AS a second stage, once piled, the material is irigated with a solution containing a high copper and chloride ion ‘concentration, aimed at producing two effects: the oxidation ‘ofthe ferrous ion to & Ferric one, and the dissolution of the ‘copper sulphides by means ofthe ferric ion thus formed. The solubilized copper is carried by te irrigating solution, and the solution flow obtained atthe exit point of the piles is ‘subjected toa copper recovery standard process, preferably ‘solvent extraction slage, followed by electrowinning ‘obtain copper eathodes, Next, these two operations are described in detail, In the current state of the ar, carrying out a previous agglomeration and curing stage ina heap leaching process of finely crashed materia, isa common practice. This concept 's valid both for oxidized materials and copper sulphide ores At this stage, two effects, highly important forthe subse- ‘quent heap leaching process, ae searched for. First, improv- ing the physical characteristics of the ore particle set by means of an agelomeration process. In this process, the % o 6 particles adhere to each other foring 4 uniform conglom- trate of particles, to form a common body thanks to the adherence mectanisms resulting from the liquid bridges due to surface tensions. Currently, his operation is carried ott in an agglomerating drum, Specially inthis process, the finer particles adhere to the larger ones thanks to this mechanism, keeping the later to be flushed away by the inrigation solution, Second, obtaining a significant and quick dissolution of the copper oxidized species present on the ore, is searched for. This is achieved by adding acid, preferably sulfuric, and ‘water inthis stage. The acid protons react withthe oxidized anions of the ore species, wenerally oxygen, hydroxide, carbonate or silicate, forming water and releasing cations such as ion, sluminum, magnesium, and other less impor- {ant ones, which are dissolved into the solution. This purely chemical concept is designated “curing” i the hydrometal- lgieal technical language Fr the frst purpose ofthe agglomeration, that i, having the particles adhered 1 each other, adding water is generally ‘enough, since this is able, by itself, to create an attraction force among the particles dve tothe generation of interface forces. In some eases, it has een necessary 10 add some binding or tensoactive agent to reinforce this effect, espe- cially with ores showing a high content of fine particles. Generally, the binding agent active principle is based on organic polymers, such as the polyacrilamides, which are formally commercialized, On the other hand, several attempls to use inorganic aerials to have the ore particles adhered, are known. Inthe gold hyerometalurgy, for example, this role can be played, and they often do, by the Portland eement and the cai bxde. For copper, where the adhesive materials, unlike the go! minerals, should be resistant tothe acid, such attempts Jnclude the gypsum, caleium oxide, some clays and others. In the process, the purpose of this invention, the same concepts 38 described above are used. That is, having the ‘concentrate particles adhered to the material working as 2 base, and quickly dissolving part of the copper contents of the oe, in this cas, specifically the copper sulphides. oth concepts are based on the results as previously ‘eseribed and presented in the Chilean Patent No. 40891, ‘which is incorporated by reference herein. To have the concentrate particles adbered to the mineral material, the same concept wsed for ores, specially those containing fine particles, is used, except that in this ease, an aagglomerating element, formed at the same place, of “in situ”, by chemical reaction of an specially added compound, is usd: the caleium chloride, reacting with the sulfuric aid, ‘which is usually added in this same instance. "The reaction as produced inthis process i the following o ‘Where the compound: CaS0,2H,0 also commercially known as gypsum, is a natural, inorganic binding material, used in this manner in various processes. denominated “eeramie” fo manufacture a large number of objects ‘The amount of caleium chloride to be added should be such that the amount of eaeium sulfate formed is enough to teaver the ofe coarse particles, for these to be able to each the concentrate finer patiles, by generating 3 “flycatcher” cect. ‘Once the concentrate particles have been caught on the ‘mineral particles, these are not mechanically released, not even with a high irrigation cate, as experimentally proved. cath $0 42,.0-080.aH1,0121aCrUS 6,926,753 B2 1 The second effect proiced in this stage ofthis invento is the quick dissolution of the concentrate components ‘containing copper. Since sulfuric acid is also added in this, ‘stage to contribute the sulfate ions required for gypsum to form, the sulfuric acid protons are also necessarily being added, which in tur combine with the oxygen in the oxides And other oxidized anions of the concenteate, to form water land release the copper citions, the same asin the normal ‘curing operation and agglomeration of the oxidized ores. In this case, however, the addition of caleium chloride produces @ much more outstanding elect, especially with the copper concentrate containing copper sulphide species ‘The effeet produced is similar to that ofthe acids on the ‘copper oxidized ows, that iS, a quick dissolution of the ‘sulphide ores, but in this ease, this works atthe same time for the oxidized ore, and this clearly makes the difference between both processes, since in the normal curing stage of| the oxidized ores, only the copper oxidized ores are dissolved, and practically none of the copper sulphides. "The cause of this phenomenon has been found alter along. research and study period, which was panially described in the Chilean Patent already mentioned, and ean be explained inthe fllowing simple manner Fin, the reaction generated to dissolve the sulphide ows ‘ean be commonly written as euSi2Fe uae? ® or al cafes Fe? -ocu 428 se ° ‘These two reactions are the most important ones in the ‘copper sulphide ore leaching, since they show that it isthe ‘oxidation of the sulfur a8 contained in the sulphides what Allows the copper to release in the form af a cation, In this ese, the ke ofthe pheoomenon isthe presence of the chlorine ion, which is contributed by the calcium chlo- ride a is clearly shown inthe equation (1) and, however, is rot showin inthe reuetions (2) sad 3) In this stage, the chloride has two effects, very different from each other, but equally important. First, the chlorine atom generates 2 apparently exypioerystlline structure of the sulfur produced by the reaction ofthe sulphides, reac- tions (2) and (3). Unlike what happens without chloride, for ‘example in a sulfate environmen, the chloride produces reaction prot layer that improves the transfer of the fetic jon, and the exit of the ferrous and the eopper fas, which are the reaction products. “This phenomeaon is well documented in various works 3s Indicted in the literature, for example, in the references. "The second effect ofthe chloride ion that of increasing the oxidation rate of the fers ion, to form a moe free ion to oxidize the copper sulphides according withthe reactions (2)and (3). Thisefect is interpreted as follows, which is also ‘deserbed on the Chilean Patent already mentioned First in the presence of chloride, unlike that what happens jn a sUlfate environment, the cuprous ion can exist in ‘equilibrium with the cupric ion due to the formation of ‘chloride complex ions. groups. AS an example, we ean, ‘mention the existence of three first cuprous chlorides, eang- ing from the lower to the higher grade ofthe complex ions CoCr © 6 © ‘where the subindex (aq) means the compound is in the aqueous phase. These equations show that, the higher the % o 8 ‘concentration of ebloine inthe solution, th higher the level of the cuprous complex ion. Likewise, the frst cupric eblorides ean be described as: CWP CHC o WSCC) © ‘Te equilibrium among these compounds can be writen {or each pair of compounds, for example between the Wo fist ones with the lowest eblorine coatent, as follows: Cag HO” on This is a halfcell reaction; another reaction, able 10 ‘consume the electron Formed through this reaction, thats, 2 reaction with an eleetron acoeptor eompound, is required ‘The most evident candidate & tho atmospheric oxygen, entering info the solution, forming water, and using hese two electrons: i010 ow [By using this equation, the equilibrium between the cuprous chloride complex ion and the euprc chloride com- plex ion, should be writen as: 2g DHOHO, DOHC gg ALO on Inthis reaction, the oxidation of a compound, the cuprous ‘complex. ion, takes place, giving rise to an oxidized ‘compound, the complex cupric inn, and this oxidation eam be used, in tru, to oxidize the copper sulphides, for example: S20 -20UC yh" on a this equation, the cupric ion has been weitten in a monomeric way, because this i the way it found in the sulfur. However, it is possible that this same ion is able 10 oxidize part of the sulphide sulfur and, therefore, less ehloride-cuprie complex ioa is used to oxidize the sulphide. ‘Thal is, the mechanism works according to the following reaction: OS H0UC OC HOWS* 9 “This gives cise othe Formation of the cuprous ion, rather than the cupric ion, like in the reaction above. Even though the previous reactions are theemodynsmically feasible, in the presence of iron ia the solution, the most likely eeaction forthe sulphide leaching involves the fevic jon. Thete are ‘wo strong retsons lo slate this: first, the oxidation potential ofthe electrochemical couple: fericferrous is higher than the: cupric-cuprous couple. Second, the Terrie ion a smaller and more active ion than the groups containing the cupric complex ion, so, the electron acceptor is likely to be the ferric in, according to the following reaction mene 9 ‘With this, the equilibrium between the cuprous complex. {on and the cupric complex ion can be weitten as 20 PCH FE oo ere, the cupric ion has been reduced to cuprows, and the {erous ion has oxidized to ferric, and his latter reacts with the copper sulphides according 16 the reactions (2) and (3), 8 st forth above,US 6,926,753 B2 7 According to all that stated, the system that has two ‘electrochemical couples, that is, the hloride-cupric ‘’chloride-cuprous, and the feeiefertous couple works 38 follows: ‘The chloride-cuprous complex ion reacts with the almo= spheric oxygen according to reaction (12) to form chloride ‘eupeic complex ion ‘The chloride-cuprie complex ion reacts with the ferrous Jon according 10 the equilibrium reaction (16) to form the ferric ion, also forming the ebloride-cuprous complex ion as product Of the reaction, whieh oxidizes back with the imospheric oxygen according Io reaction (12) The ferric ion generated in the previous reaction attacks the copper sulphides, according to reactions (2) and (3), releasing the copper ions contained in them, towards the solution In this reaction, the ferric ion is redueed to ferrous fon. ‘This ferrous ion oxidizes back, according to the equilibrium 09). “This mechanism corresponds to a self-atalytieresction, singe the reagenis aevessary for the final mechanism are intemal generated io the sume reaction system, ‘These same reactions take place with the more complex. forms of euprous and cuprie ions, but the resull isthe same, that is, the oxidation of the Ferrous ion to feric ion as catalyzed by the cupric ion, resulting in the euprous ion, ‘which easily oxidizes withthe ai, ‘Obviously, the execution of the process deseribed in this jnvention is independent of the chemical mechanism that sctually takes place, and the above represents the best vision ‘of the authors with the sale purpose of physically and ‘chemicilly explaining the untstal phenomenon, From a practical point of view, the industrial process as, produced by the chemical reactions previously described cat bre deseribed through two characteristics ‘A stony material, formed by an ore, gravel, barea, oF ‘other material of similar ebaractrisies, with a typical size range of less than %" of diameter, surtounded by fine ‘material of a'size typically smaller tha Tyler 100 mesh, ‘where both materials arc adhered by calcium sulfa atural adhesive ‘A thin layer of liquid surrounding the previous adored particles, containing a gyeat amount of copper and irom in Solution in all its valence status, in addition fo a high coatent ‘of chloride ion, ‘Tis process is called “agglutination” ‘Whe this material is irigated in the traditional way ofthe Stockpile leching, all the eopper produeed io the aggut nation stage is assimilated by the iergating solution, thus producing a high capper reeovery at the beginaing of the leaching. ‘Also, after this strong attack by the sulfuric acid along wit the chloride ion being added, al the material, both that used as base and that adhered to the stony particles, has become susceptible 1 a higher reaction, following the Same reactions previously described during the leaching stage, approximately, that is, while the soli mixture is irrigated ‘witha high concentration solution of copper, chloride, ion, and acid, which are the reagents required by the leaching reactions. For the process 10 work as deseribed above, the coexist- ‘ence of all the species already mentioned is enough, that is, a base materia, a fine material containing copper, the jam chloride salt in aqueous solution, and sulfuric acd Jn any of its commercial forms. The proportions to be wsed among these components will depen on the physical cha acteristics of the two solid materials, and on the reslis ‘expected, and will not be restricted by the characteristics of the process % o 10 ‘The criterion to add the sulfuric aid is the same currently used forthe oxidized copper ores. This is generally based on ‘experimental sts, and the final result depends on each ore, or in this case, of each concentrate. A typical criterion ‘consists of adding, in this stage, 80% of the acid which will be consumed by the gangue, plus the acid that will be consumed by the copper in the agglomeration o¢ curing stage. For example, un ore containing 1.5% of copper, where the recovery in the curing is assumed to be of 306%, it requires 7 Kgiton of acid because of the copper. If furthermore, this ore shows an acid consumption of 30 Kgiion of gangue consumption, then, the amount of acid 10 be adked in this stage should be about 31 Kgyton of acd. ‘The amount of acid added to the curing stage limits the amount of CaCI, that can be added, Infact, if the amount of acid is M_ Kg/ton, then there exists, as 1 maximum, 30 Kgiton of sulfste’ jon available to form CaS0,*2H.0. Therefore, according to reaction (1), the amount of CaCl likely to be added is 35 Kwton. If larger amount is added, part of the CaCl, will not react, and its role will be useless, "This value represents the maximum amount of CaCls 0 bbe added to the ore, which isa function of the amount of acid adked! in the curing stage. On the other hand, the miaimum amount of CaCl, to be added is a function of the surface of the particles of the material used as a base, which are able to form growth cores with the fine particles. For example, if «typical distribution of an ore under 4" is used, and the particles able to form cores are supposed 10 be those larger than 2 mm, then the specific surface of these core-forming. particles will be in the neighborhood of 2.7 [em*/g] of ore. “Another criterion for the amount of calcium chloride tobe added could be the following: For the calcium sulfate 10 exer ils “flycatcher” effect already described, this should ‘completely surround the particles ofthe base material which generates nucleation, For this effect to be as expected, it can be assumed thatthe calcium sulfate layer should be able 10 retain half ofthe largest volume of a concentrate particle. IP the largest particle of eoncentrate is 100 mierons, then the sulfate layer should be, as a minimum, 0.005 em. thick. jven this value, the gypsum volume required for this distribution of base material particles should be 0.0135 [em*/g]. Assuming s density of 2.0 [giem*] forthe hydrated ‘gypsum, this means that 0.027 g of gypsum per gram of ore is beeded to obtain the effect desired, Using the proportion of gypsum formed regarding the calcium chloride added, according to reaction (1), an amount of 17.4 Kg of CaCl per ton of ore is obtained, ‘These values are given only as an example of how to calculate the amounts of sulfurie acid and calcium chloride to be used in each case, not as limitation to our invention. ‘Cases more complex than this may exist, which should be specially analyzed. The amounts of sulfuric acid and cal- cium chloride to be added will depend on each ease, and should be experimentally studied. ‘Also, our calculations show that this process is valid to try any materials containing copper, regarlless if it has its origin, {in an oxidized, pure material, ora sulphide. The rationale of the process isthe following: the calcium sulfate as formed, ‘due to the caleium chloride added, is more than enough for ‘the material formed by this method to be able to form & leaching heap. ‘Numeric values of the typical amounts of the different ‘components used up to this moment are shawn below, in the application example section. Proferred Realization of the Invention ‘The preferred realization of this invention consists in ing the base material, which will wsvally be sevaller thanUS 6,926,753 B2 i 4, preferably under 16" and, even beter, less than %, with 2 fine material that will usually be smaller than Tylee 100 ‘mesh, ad will be the one containing the valuable copper species, specifically copper sulphide compounds. Its not Timited 10 the Tater, since oxidized species can also exis ‘easily soluble or refractory, and also pure copper or slightly ‘oxidized, in which case the calcium chloride also serves 10 adhere these pacicles to the base materia The mixture of these two solid materials along with sulfuric acid and the calcium chloride solution, or slid calcium chloride dissolved in water, takes place preferably Jno a rotatory drum to form the aglutinated material, which Js arranged in eaps, in the traditional way, atthe current hhydrometallurgical plants APPLICATION OF EXAMPLES. A high number of experiences using the concept previ= ‘ously described have been realized, both in industrial size heaps and columns, as well as with different material, hoth forthe base material, that, ore or barren material, and the fine material adhered to said base, Next, the more significant ‘examples, at our judgment, of these experimental tess, are ‘shown, Example No. 1 In this example, two semisindustrial heaps, 1,000 tons ‘each, were formed, mixing a low grade ore from the ore body Estefania of Minera Michila, with the following ‘chemical characteristics, was mixed: total Cu: 0.52%; salible Cu: 0.30%, and an acid consumption por laboratory test of 90 Kgfon, this ore was used as base material, It was mixed with a concentete, ia two dilferem proportions, in a stockpile with 6.9%, and the other one with 10.1%. This concentrate had the following characteristies: total (Cun26.10%% soluble Cu7.27%, and an acid consump al the laboratory of 150 Keston. According tothe mineralogical analysis, the sulphide part of this concentrate is mainly ‘composed of caleosine, around 85%, and the rest is com= posed of eoveline, borite, and in lawer degree of chaleopy- Fite The particles size distribution, with ils respective cop- per grade, of the concentrate and the ore, were the follwing: CONCENTRATE PARTICLES SIZE DISTRIBUTION | acoumlasd “Wel “Us “tal 420 md SS ae = Mob _Paril_Assmltsd —“S] Us) % o 12 -continved ~ OR PARTICLES SIZE DISTRIBUTION % % GOT %OS FOm Me Ponal _Accumnbtes “TS Tet TL The ore was fed, along with the concentrate, «© an industrial rotatory drum ata mass rate of 320 tony. At the same time, along with the ore and the concentrate, sulfuric ‘cid was ade! through a pipe at arate of 30 Kelton of ore In the normal operation of this industrial rotatory drum, ‘normally at the plant, sea water is also used at arate of 66) tom of ore. In this case, water was totally replaced For a sea ‘water and calcium chloride solution, which is soluble in water, ata concentration of200 gilt of calcium chloride used in this study. The amount of the solution used in this ease \was 84 Iltoa of ore higher than the aormal amount of water used due fo the water consumption of the reactions of this process, explained above, To supply the concentrate, a side belt that fed 90° above the ore main belt was used, which discharged directly into the rotatory drum, as shown in FIG. 1. In general, the process was similar to what is usually carried out ithe formal ore agglomeration work site, being the addition of| the calcium chloride solution eather than sea water, a in the usual practice, the only significant dilerenee. “Two heaps, each being about 1,000 tons, were loaded with the material from the agglomeration drum. The heaps began being irrigated with a solution that contained an average of| 4 gilt of chloride and 7 git of copper, approximately. During the whole leaching period, the solution flow that entered into the heaps was measured, and each certain number of days, usually three, the concentrations of a ‘composite atthe entrance and exit of the piles were me: sured, Afier some lime, around 110 days, the heaps Were ischarged and the leached gravel was analyzed for total copper and soluble copper. This allowed to calculate the recoveries per head/-al of both stockpiles, FIG. 4 shows the recoveries obtained for both piles, which turned out to be 93.7% in both eases, value obtained from the head-gravel gras at both pies. The bead grades were: 2.17 and 3.00% of total Cu respectively, and the coerespond- ing leached gravely: 0.136% and 0.187% of total Cx, ‘The value for the recovery as indicated above, come spon tothe recovery of the mixture of the low grade ore ‘with the concentrate. Here, it 8 not possible to know in advance which recovery corresponds tthe ore, and which ‘one corresponds to the concentrate, since we do not know ‘which part of the copper in theresa gravel corresponds {0 the ore, and which one corresponds 10 the concentrate The only thing to do is an estimation ofthe recoveries of both components of the mixture, as shown below. Fits if the gravel grade is assumed to be the same for both materials, then the recovery obtained forthe ore being 739%, and 99.5% for the concentrate. This value seems 10 be very optimistic, in spite ofthe ecovery of the ore is quite suitable for its head grade, However, on the other hand, i the smallest size part ofthe gravels tha is, that under the mesh 654 is assumed lo fully correspond tothe concentrate, then the new resulls ate: the recoveries oblained Tor the ore Amount fo $3.3 and 80.0% for cach ofthe piles, and 968 and 96.7% of total copper inthe concentrate fr ea ofthe ples.US 6,926,753 B2 a ‘The real result for the recovery of total copper ia the ‘concentrate has to be between these two values that is, between 96.8 and 99.5%, In both cases, the recoveries obtained are comparable (0 the recovery ablained in a pyrometallurgical prosess. Example No. 2 ‘To show that this process is also applicable © other ‘copper species, not only those of the chaleocite type as seen in the previous example other experience was realized with ‘concentrate from the flotation of copper slag smelting. This, new concentrate had the following global characteristics: Chemical composition: 31.28% of Tol Cu, 330% of Soluble Cu; 23.4% of Total Fe, and 8.11%, of Soluble Fe, {and a laboratory aed consumption of 9.0 Kg of acid per Ke ‘of Soluble Cu, The particle size analysis gave the following. values: Mn Min «OT OS ROM "= ete ‘The mineralogical analysis, onthe other hand, recognized the presence of the following species: Chaleopyrite: 60%, Chaleocite 24.1%, Covelin: 1.6%, Bornite: 5.2% with some Pyrite (6.7%) and pyrshotite (<25). 1s aso interesting 10 ‘tae thatthe X-Ray analysis of this sample indicates that uch of the copper sulphides are amorphous, that is, 00 ystallin, and the res in the form of chalcopyrite Tis concentrate was mixed in the proportion of 11.0%, ‘on wet base, with an ore that had the Following geain size sdstebution: sass Paral Ascomiues “Tel Ee) Ed The mixture took place in a homogenizer drum before the agglutination, The bead grase of the mixture atthe end of| this process tured out o be: 3.901% of total Cu, 0.503% of soluble Cu, and 3.397% of insoluble Cu. The mixture was made by adding 15.0 Kg/ton of calcium chloride in an aqueous solution of 150 gi of chlorine. The amount of industrial sulfuric acid added was of 30 Kg/ton, Finally, sea ‘water enough to each a toal of 100 Kg_ton of humidity was added. With the material agglomerated inthis way, a column of ‘3 mheight, and 19 cm diameter, was loaded, Two days later, the column began being irigated a rate of 20 lim? hr with a solution that had, as its main components, the following: (Cu: 4.7 gilt Toll Per 118 git, Fes 8.3 gilt, acid: 73 gt y C1: 95 gi At he end ofthe leaching period tis solution % 14 was changed with another that contained only 0.7 git of ‘copper for the purpose of eliminating, by washing, the ‘copper that remained soaking inthe agglomerate at the end ofthe leaching. FIG. $ shows the recovery curve obtained, where the final recovery of 90.2%, whieh corresponds toa gravel grade of ‘OS8¥%¢ of Total Copper, can be seen, The evident increase of the recovery atthe final part ofthe curve is due to the cllect of the washing already mentioned. Again, there is a problem to estimate the reccvery of each of the materials involved, since thete is only one gravel agra. Like the previous case, the til grade can be assumed to be the same forthe material and forthe concentrate, with Which 4 98.8% recovery is obitined forthe concentrate, and {66.4% for the ore. However, this calculation gives 4 100 ‘optimistic value. A more pessimistic exereise can be done, by considering that all ofthe gravels under the mesh —1008 correspond to concentrate, ‘The recoveries asined, in this cease, ate: 91% for the eoncenteate, and 80% forthe or. The process deserved hereby is proven tobe industrially applicable tthe material of the characteristics deseribed, ‘that is, material rom flotation of eopper slag melting. Again, the only role of the ore used is Keeping, helped by the calcium ehioride, the concentrate particles trom being swept by the irsigation solution. IT an inert material, without copper, is used rather than ore, the role played isthe same, with the additional advantage of solving the issue of the recovery assignment, since that of this material would be Example No. 3 Finally an example forthe copper material more dificult to leach, corresponding to a concentrate mainly composed of chalcopyrite, is included. With this example, the: process eseribed heteby is proven to be worthy forall the types of ‘copper sulphide concentrates. The chalcopyrite concentrate used had the following characteristics! Globil chemical composition: 45.36% of ‘Total Cu, 280% of Soluble Cu; 16.5% of Total Fe, 0.8% of Soluble Fe, and a laboratory acid consumption of 16.0 Kg of acid per Kg of Soluble Cu. ‘The grain size analysis gave the following values: Mer ae El 000 om aoe tk ae 2 tie 858100 18 On the other hand, the mineralogical analysis showed the presence of the following species: Chaleopyrite: 65.2%, Digenite: 25.1%, Coveline: 77%, bornite: 2.0%, and some pyrite (2.6%). lis also interesting to stress the fat that the X-Ray analysis of this sample showed that large prt ofthe sulphides correspond to chalcopyrite. Previous results show that the non-chalcopyrite copper content reaches 56.4%. So, any recoveries obtained above this value means that a part of the chalcopyrite has been leached. ‘The chaleopyrite concentrate was mixed in 11.0% proportion, on wet base, with an ore having the following particle size distbution:US 6,926,753 B2 15, % SGT &O8 SOM Mest Paial Assumed “Ist eal 10000 nas 019 ass Like in he previous example, the mixture took place into anhomogenizer drum before the agglutination. The grade of the resuling product was 5.2% of total Cu. Agghtintion was obtained by adding 15.0 Kston of calcium ehlride in 2m aqueous solution of 237 ait of calium chloride. The out of instil sfc sei added was 30 Kyo, 3nd finally, sea water enough to reach a total humty of 100 kgton of water was added ‘With the material agglutinated in this way, a column of 25 tm height, and 19 cm diameter was loaded Two days lar, the column began being gated ata rate of 20m he with ‘solution containing, asthe mest important components the following: Cu: 47 gilt Total Fe: 18 gt, ferrous on: 83 ‘placid: 7.3 pit and Cl 95 g/h. At the end ofthe leaching Petid, this solution was replaced with aother one cootine Ing only 0.7 wit of copper to wash away the copper that femmained soaking in the agglomerate at the end of the leaching. Washing continued for 28 days IG. 5 shows the recovery curve obained, where final recovery of 85 5% can be sen, fra gravel rade of 0.76% ‘of otal Cu, The evident increase of the recovery a the final part of the curve is de tothe wash ellets, mentioned shove Again, there is a problem to estimate the covery of each ‘of the materials invobed, sige there is only one gravel gyade. Like inthe provios case, the gravel grade ean be Supposed to the same forthe ore athe concentrate. In this cease, a eeovery of 29408 forthe or, aad 98.3% for the ‘concentrate is obtained, but this calculation gives a {00 ‘optimise value. A more pessimisic supposition can be ade, by assuming that all he gravels under mesh —100 Belong to the cooeentate, Tn this ease, the recoveries ‘obtained ace: 78.9% forthe concentrate, and 64.8% forthe This example shows that the proces is also industrially applicable to concentates of eblcopyrie oes. Ago, the nly sole ofthe ore used is keping, helped by the claim chr, the eonceatrate parle from beng Swept away by the irigting solution. an inert material, witout copper, ‘suse sole isthe same, withthe additional advantage of solving the problem Belped by the calcium chloride, the onceattate particles fom heing swept away by the iil= {ng solution Ian inst material, without copper, i use is tole the sme, with the adklitional advantage of solving the problem ofreoveryasignment, sac tha ofthis ore Would be zero. ‘What has been described above ae prefeaed aspects of the present invention It is ofcourse nt possible to describe ‘every conecivable combination of eamponenis oF metbod- ‘logis for purposes of deseribng the present invention, bit ‘one of ordinary skill in the set will recognize that many furter combinations and permutations of the preset inven tion are possible. Accordingly, the present invention is 16 ended 10 embrace all such alterations, combinations, ‘mesiicatons, and variations that fall within the spirit and scope of the appended claims. We claim 5 LA procedure to leach copper flotation concentrates in 8 heap, comprising the steps of anificially achering the concentrate to the surface of 3 ‘solid material, Wherein said solid material is selected from the group of materials consisting of a rocky jo Material and a plastic material, to form a chemically hered agglomerated materia; stockpiling the chemically adhered agglomerated material to form a leaching heap; and Teaching the beap with a solution containing a least Cl, Cu, and Fe ions. 2. The procedure according 1 claim 1, further comprising the steps of simultaneously mixing of ‘the rocky material having a size typically less than % inch ‘wilh 2 copper concentrate in a weight fraction up to 20% to form a mixture of rocky material and copper Concentrate; adding a calcium chloride solution containing 2210 250 ‘grams of ebloride per liter of solution to the mixture of rocky material and copper concentrate in a proportion ‘of 5 to 250 kilos of caleium chloride per ton of ‘concentrate; ad adding 4 second solution containing sulfate ions 10 the mixture of rocky material and copper concentrate in 3 proportion ofS to 70 kilos of sulfate per ton of mixture, ‘wherein the final mixture has moistre eontent between 35 to 130 kilos per ton of rocky materia in dry basis. 3. The procedure acoording to claim 2 wherein the ocky material size & ao greater thin 4 inc, The procedure scoring fo aim 2 when the rocky aerial size i o0 greater than % he procedure scoring toca 2 and fre inl ing the step of adding a water flow to the mixture in order togel a moisture content between 35 to 130 kilos per ton af ‘6. The procedure according to claim 2, wherein calcium chloride solution is prepazed with a water selected from the ‘oup consisting of pure water, industrial water, treated Sewage Water, a Water and saline wat 7. The procedure acconiing to claim 2, wherein the second solution containing sulfate ions is sulfuric acid, with a jeoncentration in weight ranging from L410 98%. 8. The procedure according o claim 1, wherein said rocky material is selected from the group consisting of an ore, Daren mining rock a discarded ore and a leached ore. '9. The procedure according 10 claim 2, wherein the concentrate is replaced by a material selected from the group ‘consisting of 2 copper tailing, a copper precipitate and any other dusiy material cootaining copper values, 10, The procedure according 10 claim 2, whercin the concentrate comprises copper in the form’ at least one ‘compound selected from the group consisting of chaleoci coveline, covellite, bomnite and chalcopyrite I. The procedure to leach copper concentrates on ‘non-looded heap, according to claim 2, and further inciud- ing the steps of letting the beap rest for a period ranging from 15 10 90 cays: leaching the heap during a leaching sage bys leaching, ‘solution, aa flow rate of 5 to 100 arr for a period Fanging from 50 to 300 days; and ‘once the leaching stage has finshed, washing the heap ‘washing solution at a fow rate of 5 to. 100, be for a period ranging from 1 10 30 days, % oUS 6,926,753 B2 17 12. The procedure o leach copper concentrates, agglom- ated according to claim 2, on 2 non-looded heap accord ing to claim 11, wherein the leaching solution contains between 05 and 10 gt of eopper, between 50 and 120 gt ‘of chloride, and 5 10 25 git of equivalent sulfuric concen= 13. The procedure according to claim I, wherein the leaching solation is formed from a misture of pregnant and raffinate solutions of the process. 14. The procedure according to claim 11, wherein the ‘calcium chloride added in the agglomeration Stage contrib lules part or all ofthe chlorine of the leaching solution, 18, 15, The procedure according to claim 11, wherein the washing solotion is rafinate solution 16, The procedure according fo claim 15, wherein the raffnate solution contains between (and I git of copper, between 60 and 130 git of chloride, and 10 10 40 gilt of equivalent sulfuric acid concentration, 17. The procedure according to claim 1, wherein the plastic material are a polyethylene sphere packing.