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US 20160194771A1 (19) United States (2) Patent Application Publication (10) Pub. No.: US 2016/0194771 A1 SCHUFFER AMELLER (43) Pub. Date: Jul. 7, 2016

(54) USE OF OXYGENATED OR Publication Classification POLYOXYGENATED WEAKACIDS, OR , COMPOUNDS ORDERIVATIVES (51) Int. Cl. C25C I/IX (2006.01) THAT GENERATE SAME, IN COPPER (52) U.S. CI. ELECTROWINNING PROCESSES IN CPC ..…. C25C 1/12 (2013.01) CATHODES OR ANODES OF ELECTROLYTIC CELLS, ORIGINATING (57) ABSTRACT FROM THE LEACHING OF A COPPER The invention relates to the use of oxygenated or polyoxy genated weak acids, or minerals or compounds that generate the same to stabilize and buffer the electrolyte solution, (71) Applicant: QUIBORAX S.A., Vitacura, Santiago thereby improving its conductivity, and/or catalytically pro (CL) moting copper electrodeposition. Additionally, a copper electrowinning procedure is described (72) Inventor: Carlos SCHUFFER AMELLER, Arica that comprises the addition of a necessary quantity of an (CL) oxygenated or polyoxygenated weak acid, or mineral or com pound that generates the same, to the electrodeposition pro (21) Appl. No.: 14/758,152 cess; wherein the necessary quantity of weak acid will depend on the characteristics of the mineral, the electrolyte solution, (22) PCT Filed: Dec. 27, 2013 and the current density used. In the invention, the addition of oxygenated or polyoxygen (86) PCT No.: PCT/CL2013/000098 ated weak acids, minerals, compounds or derivatives that § 371 (c)(1), generate the same to the charged electrolytes coming from the (2) Date: Jun. 26, 2015 solvent extraction phase and entering the electrowinning (EW) stage serves the purpose of homogenizing the current (30) Foreign Application Priority Data density within the electrolytic cell, resulting in increased electrical energy consumption efficiency versus the amount Dec. 28, 2012 (CL) ..… 3726-2012 of copper deposited. Patent Application Publication Jul. 7, 2016 Sheet 1 of 2 US 2016/0194771 A1

Figure 1

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3. ?urrett density A.3. Patent Application Publication Jul. 7, 2016 Sheet 2 of 2 US 2016/0194771 A1

Figure 2

£attent density Ajmº US 2016/0194771 A1 Jul. 7, 2016

USE OF OXYGENATED OR ers. Filters are used to achieve a better effect with two units POLYOXYGENATED WEAKACIDS, OR (electrowinning cells), instead of one. MINERALS, COMPOUNDS OR DERIVATIVES [0012] b) Electrical connection characteristics: Electrow THAT GENERATE SAME, IN COPPER inning cell electrical connections are very simple, since they ELECTROWINNING PROCESSES IN attempt to reduce the distances from rectifiers in direct cur CATHODES OR ANODES OF rent and high voltage. ELECTROLYTIC CELLS, ORIGINATING [0013] The energy requirements, particularly for electrical FROM THE LEACHING OF A COPPER current, necessary for the electrowinning process are signifi MINERAL cantly high compared to other types of industries. The inven tion is directed to make electrical energy consumption in [0001] The invention relates to the use of oxygenated or copper mining more efficient, particularly in the electrowin polyoxygenated weak acids, minerals, compounds or deriva ning process, thereby solving a problem widely recognized in tives that generate the same, at any degree of concentration, in the industry. copper electrowinning processes in cathodes or anodes of [0014] Metal electrowinning is governed by Faraday’s electrolytic cells from an electrolyte charged with copper Law, which states that: sulfate originating from the leaching of a copper mineral. [0015] The amount of chemical change produced by an [0002] The invention relates to the addition of oxygenated electrical current, i.e., the dissolved ordeposited amount or polyoxygenated weak acids, minerals, compounds or of a substance, is proportional to the amount of electric derivatives that generate the same, to the charged electrolytes ity passed. coming from the solvent extraction phase and entering the electrowinning (EW) stage in order to homogenize the cur [0016] The amounts of various substances deposited or rent density within the electrolytic cell, resulting in increased dissolved by the same amount of electricity are propor electrical energy consumption efficiency versus the amount tional to their equivalent chemical weights. of copper deposited. [0017|| Faraday’s Law states: [0003] Electrowinning (EW) or electrodeposition is one of the processes to recover-in pure form and selectively-metals that are in solution, and consists of recovering the metal from md = ºrrº. = QTC – CFl a properly conditioned leach solution (electrolyte solution), and depositing it on a cathode using an electrolysis process. [0004] In the copper production process, electrowinning is [0018] Where: a highly relevant stage, as copper for industrial use requires a [0019] md=mass deposited [mass/time] purity grade established by electrolytic copper standards. [0020 P., Emolecular weight of the element in study [0005] In the electrowinning (EW) process, a direct electric [0021] iºn-current density of the cell current of low voltage and high intensity circulates through [0022] A.-total area exposed to deposition the electrolytic solution between an anode, the solution itself, [0023] t-exposure time and a cathode. In this way, the metalions of interest (cations) [0024] m. current efficiency (90-92%) are attracted to the cathode (negatively charged pole), where [0025] Z=number of electrons exchanged in the deposition they are deposited, and the impurities are dissolved in the reaction. electrolyte solution, or are precipitated as residue or anode [0026] F=Faraday constant (96.500[c/g-eq] slimes. [0027] Q=solution volumetric flow [0006] Through the electrowinning process, it is possible to [0028] [C-CA-change in concentration of the element of recover metals-such as copper, gold, and silver-from leach interest in the electrowinning stage. able resources that would otherwise be unfeasible. [0029] The role played by oxygenated or polyoxygenated [0007] The processes of purification and concentration of weak acids-such as boric acid or orthophosphoric acid-, min leach solutions, such as solvent extraction (SX) for copper erals, compounds or derivatives of the same, at any degree of and activated carbon (AC) for gold, have broadened the scope concentration in the electrowinning processes of metalions in of application of the electrowinning process to recover these cathodes has a relationship with stabilizing and buffering the metals. So much so that some metals, like zinc, rely almost electrolyte solution, improving its conductivity, especially in exclusively on electrowinning to achieve a recovery that is near-surface electrode layers, as well as catalytically promot economically viable. ing electrodeposition, even in processes with high current [0008] The electrowinning process is also a very competi intensity and high speed cation deposition. tive alternative to treat copper-cobalt and nickel-cobalt com [0030] Additionally, it controls and stabilizes the system’s bined minerals. ion discharge, as well as the homogenous distribu [0009] To perform the electrowinning process, electrolytic tion of current in the electrolytic cell, making current use cells with electric circuitry are required to circulate a direct more efficient. electric current of low voltage and high intensity. [0031] The invention relates to the use of oxygenated or [0010) So that the process is carried out efficiently, the polyoxygenated weak acids, preferably, but not limited to following aspects must be considered: boric acid and orthophosphoric acid in the copper electrow [0011] a) Circuit Configuration: To provide the direct cur inning process in order to homogenize the current density in rent required by the electrolysis process, current rectifier the electrolytic cell, resulting in increased electrical energy equipment is used to maintain constant electrical flow char consumption efficiency versus the amount of copper depos acteristics. The technology of rectifiers has evolved, and cur ited. rently uses transistorized transformer rectifiers. The filter [0032] The invention also relates to a copper electrowin requirements for harmonic current control currently consti ning process using oxygenated or polyoxygenated weak acid, tute the major factors in the increasing costs of these rectifi or a mineral or compound that generates the same on the spot, US 2016/0194771 A1 Jul. 7, 2016

whereby increased electrical energy consumption efficiency novskite, kuksite, lacroixite, landesite, laubmanite, laueite, versus the amount of copper deposited is achieved. lazulite, lehnerite, lermontovite, leucophosphite, libethenite, [0033] In the invention, boric acid refers to HaBOs (triox likasite, lipscombite, liroconite, , lithiophospha oboric (III) acid, B(OH)3, also called orthoboric acid), or their tite, lithiophosphate, lomonosovite, ludlamite, luneburgite, derivatives. minerals refers, without limitation, to magniotriplite, mahlmoodite, mangangordonite, , ulexite, colemanite, kernite, pandermite, bakerite, datolite, matulaite, metaankoleite, metaswitzerite, metatorbenite, elbaite, admontite, aksaite, ameghinite, ammonioborite, metavariscite, metavauxite, mimetite, mitridatite, , aristarainite, avogadrite, aximite, bandylite, barberiite, behier monetite, montebrasite, montgomerite, moraesite, ite, berborite, biringuccite, boracite, boralsilite, borax, bora moreauite, morinite, mundite, nabaphite, nafedovite, mali zon, borcarite, bormuscovite, cahnite, calciborite, carbob poite, nasicon, nastrophite, matrophilite, matrophosphato, orite, chambersite, charlesite, congolite, danburite, datolite, nefedovite, newberyite, niahite, ningyoite, nissonite, olym diomignite, dravite, dumortierite, eremeevite, ericaite, ezcur pite, overite, oxyapatite, parafransoletite, parahopeite, rite, fabianite, ferruccite, flolovite, fluoborite, foitite, frolov paravauxite, parsonite, paulkellerite, petersite, phospham ite, garrelsite, gaudefroyite, ginorite, gowerite, halurgite, mite, phosphoellenbergerite, phosphoferrite, phosphofibrite, hambergite, heidormite, henmilite, hexahydroborite, phosphophyllite, phosphorroslerite, , phos hydroboracite, hydrochlorborite, hilgardite, holtite, howlite, phovanadylite, phosphuranylite, phosinaite, phuralumite, hulsite, hungchaoite, inderborite, inderite, inyoite, jereme phurcalite, pyromorphite, pyrophosphite, plumbogummite, jevite, jimboite, kalborsite, karlite, katoite, kornerupine, pretulite, pseudolaueite, pseudomalachite, , kotoite, kurnakovite, lardarellite, ludwigite, lueneburgite, reichenbachite, robertsite, rockbridgeite, rodolicoite, sabu luidwigite, manandonite, mcallisterite, metaborite, meyer galite, saleeite, sampleite, satterlyite, scholzite, schreibersite, hofferite, moydite, nasinite, nifontovite, nobleite, norden scorzalite, seamanite, segelerite, senegalite, sengalite, skjoeldine, olenite, oyelite, painite, pentahydroborate, pin sidorenkite, sieleckiite, sigloite, silicocarnotite, spencerite, noite, povondraite, preobrazhenskite, priceite, pringleite, stercorite, stewartite, , strunzite, , svanberg probertite, reedmergnerite, rhodozite, rivadavite, roweite, ite, Switzerite, taranakite, tarbuttite tavorite, threadgoldite, sabinite, sakhite, santite, sassolite, shorgite, schorl, seaman tinsleyite, tinticite, triangulite, , , , ite, searlesite, serendibite, sibirskite, sinhalite, solongoite, trolleite, , uralolite, ushkovite, vanmeerscheite, spurrite, stillwellite, strontioborite, studenitsite, sturmanite, , varulite, Vashegyite, vayrynenite, veszelyite, viit suanite, sulfoborite, , Szaibelyite, teepleite, terts aniemiite, vitusita, , vochtenite, voggite, vuonne chite, tincalconite, tunellite, tusionite, tyretskite, uralborite, mite, Vyacheslavite, wagnerite, wardite, , whitmor veatchite, boric vesuvianite, vistepite, Volkovskite, vonsen eite, wolfeite, woodhouseite, wooldridgeite, ximengite, ite, warwickite, wawayandaite, wighmanite, wiluite, and wis zairite, zapatalite, zodacite. erite, among others. [0036) In general, the solutions proposed by the industry to reduce the amount of energy (such as electric current) are [0034] Boron compounds refers, without limitation, to aimed at physical changes in the electrowinning process. borax (Na2B4O7.10H2O or pentahydrate, borate, However, the use of weak acids, such as boric or phosphoric sodium tetraborate, sodium heptaoxotetraborate), borates acid, to stabilize and buffer the electrolyte solution to improve (compounds that contain boron oxoanions, with boron in its conductivity has not been described. oxidation state +3), boranes (boron hydrides). [0037] In U.S. Pat. No. 5,882,502 an electrochemical sys [0035) In the invention, phosphoric acid refers to HAPOa. tem that allows metals from other compounds to be separated (sometimes called orthophosphoric acid), copper compounds and recovered through a chemical cell system consisting of an refers, without limitation, to , phosphonates, anode and a cathode with separate sections connected by a phosphoranes, phosphides, sodium hypophosphite, phos conductor is presented. Herein an alkaline electrolyte, con phine , pentafluoride, phosphorus trichlo sisting of ammonium, ammonium sulfate, or ammonium ride, hexafluorophosphoric acid, phosphorus (III) and (V) chloride, the metalion to separate, and a halogen ion, such as oxide, among others. Phosphorus minerals refers, without bromine or a boron compound, as a reaction catalyst, is limitation, to phosphoric rocks, such as, for example, lignite, described. The extraction is from metal , particularly andalusite, aheylite, aldermanite, alforsite, alluaudite, alth nickel, cobalt, and copper. ausite, amblygonite, anapaite, , arctite, ardealite, [0038] However, in U.S. Pat. No. 5,882,502, no reference is arupite, augelite, autunite, babefphite, barbosalite, baricite, made to particular boron compounds, let alone to the possi barringerite, bassetite, bauxite, bearthite, belovite, benauite, bility of the presence of a weak acid such as boric or phos , berlinite, bermanite, bertossaite, beryllonite, beusite, biphosphamite, bobierrite, boggildite, bonshtedtite, phoric acid, nor specific compounds that can be used. As a brabantite, bradleyite, , brianite, britholite, Brush result, the choice of a weak acid, or a mineral that generates ite, buchwaldite, cacoxenite, canaphite, cassidyite, chalcosid the same is not made clearly therein. erite, cheralite, churchite, chlorapatite, coffinite, collinsite, [0039] Borate compounds are used in the non-metallic min coeruleolactite, corkite, cornetite, crandallite, crawfordite, ing industry. One of the main boron compound minerals is curetonite, cyrilovite, diadochite, dittmarite, dorfmanite, duf ulexite (NaCaBsO3.8H2O); this naturally-occurring borate is renite, dumontite, earlshannonite, ehrleite, , fair used in non-metallic mining to produce or extract boric acid, fieldite, farringtonite, florencite, fluellite, , fluo borax, and other derivatives. rellestadite, foggite, formacite, francoanellite, fransoletite, [0040] The use of ulexite has been described on the indus frondelite, furongite, gainesite, galileiite, gatehouseite, trial manufacturing level in agriculture and forestry as fertil gatumbaite, giniite, girvasite, glucine, gorceixite, gordonite, izer material. goyazite, , grattarolaite, grayite, hentschelite, herd [0041] Other boron derivatives, such as borax and boric erite, heterosite, hinsdalite, holtedahlite, hopeite, hotsonite, acid have been used as and preservatives in the food hureaulite, hurlbutite, hydroxylapatite, hydroxylherderite, industry. hydroxyl-piromorphite, isokite, jagowerite, kaluginite, kidw [0042] Additionally, borax, which is a soluble borate, is ellite, kingite, kingsmountite, kintoreite, kleemanite, kolbec used in mining together with ammonium as an and steel kite, koninckite, kosmarite, kovdorskite, kribergite, kryzha smelting mixture due to its ability to reduce the mixture US 2016/0194771 A1 Jul. 7, 2016 melting point and thereby eliminate the iron oxide contami density applied. Thus, in the system with a current density of nant from the system. Additionally, the use of borax has been 320 A/mt, under normal conditions the deposited mass was described in the smelting of gold and silver jewelry. observed to be 21.83 g, while the addition of boric acid [0043] Boric acid, as such, is used in the manufacture of increased the amount to 22.65 g (Table 1). When the cathode fiberglass, fire retardants, borosilicate glass, soaps, deter was operated at a current density of 390 A/m’, a copper gents, and certain pharmaceutical products. With regard to deposit of 2.4416 g/h was obtained in the normal system boric acid, it is used as an antiseptic, an antibacterial, to without boric acid, in contrast to the 2.4896 g/h deposited formulate insecticides, as well as in buffer solution com with the addition of boric acid to the cathode (Table 2). pounds and as a food preservative. Industrially, boric acid is recognized as raw material in the manufacture of the monofi TABLE 1 bers that make up textile fiberglass, which is used as the structural base of plastics and circuitry. Additionally, the use Copper electrowinning parameters in cathodes with and of boric acid has been described as a manufacture material for without boric acid at a current density of 320Amº. dynamite and weapons of mass destruction. Cathode without Cathode with [0044) With regard to another weak acid that is particularly Parameter boric acid boric acid relevant to the invention, such as orthophosphoric acid and its Voltage 2.00 V 2.00 V derivatives, the use of polyphosphates due to their high solu Current density 320 A/m” 320 A/m? bility in concentrated liquid fertilizers has been specified, as Test time 10 hr 10 hr well as their mining and industrial use as metal chelating ER Cu Concentration 47.2 g/L 44.37 g/L agents. Additionally, the use of sodium and calcium poly EP Cu Concentration 41.31 g/L 38.45 g/L phosphates in the food industry and in detergent preparation Theoretical mass of cathode 23.59 g 23.71 g has been described. Other phosphates, in the form of ammo according to Faraday’s Law nium salts are widely used as raw material in manu Experimental mass deposited 21.83 g 22.65 g facturing. In the mining and jewelry industry, com Actual current efficiency 92.5% 95.5% pounds, such as phosphate, are used to prevent metal corrosion and to improve lubrication. Similarly, zinc [0049) Where ER is electrolyte rich, and EP is electrolyte phosphate is used to prevent metal oxidation. Finally, phos poor. phoric acid, as such, is used as an ingredient in soft drinks, as a water softener, in fertilizer and detergent production, and in TABLE 2 the mining industry as an anticorrosive and antireduction substance, and as an agent to prevent gas evaporation. Copper electrowinning parameters in cathodes with and [0045] In no case is the traditional use of oxygenated and without boric acid at a current density of 390A mº, polyoxygenated weak acids consistent with the proposed use Cathode without Cathode with and procedure of the invention. Parameter boric acid boric acid [0046] Below are examples which illustrate the significant improvement that the use of oxygenated or polyoxygenated Voltage 2.00 V 2.00 V Current density 390 A/m” 390 A/m2 weak acids, particularly boric acid, provides in the electrow Test time 10 hr 10 hr inning process. ER Cu Concentration 49.25 g/L 39.72 g/L EP Cu Concentration 41.47 g/L 32.09 g/L EXAMPLE 1 Theoretical mass of cathode 24.90 g 24.42 g according to Faraday’s Law Effect of the Addition of Boric Acid in the Copper Experimental mass deposited 24.16 g 24.2 g Electrowinning Stage in the Metal Leaching Process Actual current efficiency 97.0% 99.1% [0047] In this example, the effect of the addition of boric [0050] Where ER is electrolyte rich, and EP is electrolyte acid in the copper electrowinning process is illustrated, in poor. contrast to a test without the addition of the acid. For the electrowinning, a synthetic electrolyte solution (10 L) com [0051] In Tables 1 and 2, posed of copperpentahydrate sulfate, water, and sulfuric acid [0052] Copper experimental mass deposited=Final cath (180 g/L) was prepared. Batch tests were prepared (5 ode mass-initial cathode mass. batches), testing two systems with different current densities [0053] The experimental deposited mass is also calcu (320 and 390 A/mº.) simultaneously, with boric acid incor lated as the difference between the copper concentration porated and without adding boric acid to the cell. For each of the electrolyte rich solution and the electrolyte poor system, the voltage and amperage were set at 2V and 2 A, solution by using the following equation: respectively, allowing for continuous functioning for 10 [0054] masa.gºoga, (Cuer-Cuee)*Q*t, where Cues: is hours at room temperature. Finally, to determine the amount the copper concentration in the electrolyte rich solution; of copper electrodeposited on the cathode, the initial mass of Cuzzº is the copper concentration in the electrolyte poor the electrode was subtracted from the final mass of the elec solution; Q: electrolyte flow; tº exposure time trode. [0048] The results indicate that the proposed addition of boric acid by the inventor progressively improves the elec - - masa experimental Current efficiency = n = 100 g –—. trowinning current efficiency in comparison to the electrolyte #!Cl:Só?tegºrica solution without the addition of the acid (FIG. 1). Addition ally, electrowinning parameters in systems with different cur rent densities were measured, both with and without the addi [0055] Where: tion of boric acid during the process. As a result, an increase [0056] theoretical mass=m=I*t"eq/F, where m: electro in the copper mass deposited experimentally by adding boric chemically reactive mass; I: current intensity; t time; F: acid to the system was observed, independent of the current Faraday constant; eq; equivalents, where eq=PM/Z. US 2016/0194771 A1 Jul. 7, 2016

EXAMPLE 2 TABLE 5 Effect of the addition of orthophosphoric acid in copper electrowinning current efficiency. Effect of the Addition of Orthophosphoric Acid in Cathode with Cathode with the Copper Electrowinning Stage in the Leaching Current Cathode without orthophosphoric orthophosphoric Process. density orthophosphoric acid acid (A/m”) acid (10 mL) (20 mL) 320 92.5 A/m2 92.46 A/m2 98.76 A/m2 [0057] Following the same protocol described in Example 390 97.0 A?m2 99.85 A/m2 99.43 A/m2 1, but now using orthophosphoric acid in the copper electrow inning stage in the leaching process. [0058] Below are the results obtained, which illustrate how FIGURE DESCRIPTION a greater mass of copper deposited was obtained using this [0060] FIG.1. Effect of the addition of boric acid on current weak acid. efficiency in copper electrodeposition tests. The axes indicate current efficiency (%) with respect to current density (A/m3) TABLE 3 generated in the electrolyte solution with boric acid and with out boric acid. Where the line marked with"corresponds to the Copper electrowinning parameters in cathodes without electrolyte solution when boric acid is added to the system, orthophosphoric acid and with the addition of different volumes and the line marked with X corresponds to the electrolyte of the acid at a current density of 320 A/m”. solution without boric acid treatment. [0061] FIG. 2. Effect of the addition of orthophosphoric Cathode Cathode with acid on current efficiency in copper electrodeposition tests. without Cathode with ortho The axes indicate current efficiency (%) with respect to cur orthophosphoric orthophosphoric phosphoric rent density (A/m”) generated in the electrolyte solution with Parameter acid acid (10 mL) acid (20 mL) out orthophosphoric acid and with the addition of 10 and 20 Voltage (V) 2 2 2 mL of orthophosphoric acid. Where the line marked Current density 320 320 320 with"corresponds to the electrolyte solution without ortho (A/m”) phosphoric treatment, the line marked with X corresponds to Test time (hr) 10 10 10 the test adding 10 mL of orthophosphoric acid, and the line Theoretical mass of 23.59 23.29 23.29 marked with L corresponds to the test adding 20 mL of cathode according to orthophosphoric acid. Faraday’s Law (g) 1. Use of oxygenated or polyoxygenated weak acids, or Experimental mass 21.83 23 23 minerals or compounds that generate the same COMPRIS deposited (g) ING stabilization and buffering of the electrolyte solution, Actual current 92.5 92.4656 98.7661 thereby improving its conductivity, and/or catalytically pro efficiency (%) moting copper electrodeposition, even in processes with high current intensity and high speed cation deposition 2. Use of oxygenated or polyoxygenated weak acids, or minerals or compounds that generate the same in a copper TABLE 4 electrodeposition process of claim 1 COMPRISING a weak Copper electrowinning parameters in cathodes without acid that can be, among others, boric acid orphosphoric acid. orthophosphoric acid and with the addition of different volumes 3. Use of oxygenated or polyoxygenated weak acids, or of the acid at a current density of 390Amº. minerals or compounds that generate the same in a copper Cathode Cathode with electrodeposition process of claim 1 COMPRISING a weak without Cathode with ortho acid that is preferably boric acid, also called orthoboric acid. orthophosphoric orthophosphoric phosphoric 4. Use of oxygenated or polyoxygenated weak acids, or Parameter acid acid (10 mL) acid (20 mL) minerals or compounds that generate the same in a copper Voltage (V) 2 2 2 electrodeposition process of claim 1 COMPRISING a weak Current density 390 390 390 (A/m”) acid that is preferably phosphoric acid, also called orthophos Test time (hr) 10 10 10 phoric acid. Theoretical mass of 24.90 24.86 25.43 5. Use of oxygenated or polyoxygenated weak acids, or cathode according to Faraday’s Law (g) minerals or compounds that generate the same in a copper Experimental mass 24.16 24.82 25.28 electrodeposition process of claim 1 COMPRISING a mate deposited (g) rial containing boron or phosphorus. Actual current 97.0 99.8545 99.4295 6. Use of oxygenated or polyoxygenated weak acids, or efficiency (%) minerals or compounds that generate the same in a copper electrodeposition process of claim 1 COMPRISING a mate rial containing boron. [0059] In Table 5, the effect of the addition of orthophos 7. Use of oxygenated or polyoxygenated weak acids, or phoric acid on copper electrowinning current efficiency is minerals or compounds that generate the same in a copper described, and an increase in current efficiency by using electrodeposition process of claim 1 COMPRISING a mate orthophosphoric acid in the process can be seen. rial containing phosphorus. US 2016/0194771 A1 Jul. 7, 2016

8. Use of oxygenated or polyoxygenated weak acids, or monetite, montebrasite, montgomerite, moraesite, minerals or compounds that generate the same in a copper moreauite, morinite, mundite, nabaphite, nafedovite, mali electrodeposition process of claim 1 COMPRISING the min poite, nasicon, nastrophite, matrophilite, matrophosphato, eral boron that can be selected, without limitation, from ulex nefedovite, newberyite, niahite, ningyoite, nissonite, olym ite, colemanite, kernite, pandermite, bakerite, datolite, pite, overite, oxyapatite, parafransoletite, parahopeite, elbaite, admontite, aksaite, ameghinite, ammonioborite, paravauxite, parsonite, paulkellerite, petersite, phospham aristarainite, avogadrite, aximite, bandylite, barberiite, behier mite, phosphoellenbergerite, phosphoferrite, phosphofibrite, ite, berborite, biringuccite, boracite, boralsilite, borax, bora phosphophyllite, phosphorroslerite, phosphosiderite, phos zon, borcarite, bormuscovite, cahnite, calciborite, carbob phovanadylite, phosphuranylite, phosinaite, phuralumite, orite, chambersite, charlesite, congolite, danburite, datolite, phurcalite, pyromorphite, pyrophosphite, plumbogummite, diomignite, dravite, dumortierite, eremeevite, ericaite, ezcur pretulite, pseudolaueite, pseudomalachite, purpurite, rite, fabianite, ferruccite, flolovite, fluoborite, foitite, frolov reichenbachite, robertsite, rockbridgeite, rodolicoite, sabu ite, garrelsite, gaudefroyite, ginorite, gowerite, halurgite, galite, saleeite, sampleite, satterlyite, scholzite, schreibersite, hambergite, heidormite, henmilite, hexahydroborite, scorzalite, seamanite, segelerite, senegalite, sengalite, hydroboracite, hydrochlorborite, hilgardite, holtite, howlite, sidorenkite, sieleckiite, sigloite, silicocarnotite, spencerite, hulsite, hungchaoite, inderborite, inderite, inyoite, jereme stercorite, stewartite, strengite, strunzite, struvite, svanberg jevite, jimboite, kalborsite, karlite, katoite, kornerupine, ite, Switzerite, taranakite, tarbuttite, tavorite, threadgoldite, kotoite, kurnakovite, lardarellite, ludwigite, lueneburgite, tinsleyite, tinticite, triangulite, triphylite, triplite, triploidite, luidwigite, manandonite, mcallisterite, metaborite, meyer trolleite, turquoise, uralolite, ushkovite, vanmeerscheite, hofferite, moydite, nasinite, nifontovite, nobleite, norden variscite, varulite, Vashegyite, vayrynenite, veszelyite, viit skjoeldine, olenite, oyelite, painite, pentahydroborate, pin aniemiite, vitusita, vivianite, vochtenite, voggite, vuonne noite, povondraite, preobrazhenskite, priceite, pringleite, mite, Vyacheslavite, wagnerite, wardite, wavellite, whitmor probertite, reedmergnerite, rhodozite, rivadavite, roweite, eite, wolfeite, woodhouseite, wooldridgeite, ximengite, sabinite, sakhite, santite, sassolite, shorgite, schorl, seaman Zairite, Zapatalite, and zodacite, among others. ite, searlesite, serendibite, sibirskite, sinhalite, solongoite, 10. Use of oxygenated or polyoxygenated weak acids, or spurrite, stillwellite, strontioborite, studenitsite, sturmanite, minerals or compounds that generate the same in a copper suanite, sulfoborite, Sussexite, Szaibelyite, teepleite, terts electrodeposition process of claim 1 COMPRISING a com chite, tincalconite, tunellite, tusionite, tyretskite, uralborite, pound that can be, among others, a boron compound. veatchite, boric vesuvianite, vistepite, Volkovskite, vonsen 11. Use of oxygenated or polyoxygenated weak acids, or ite, warwickite, wawayandaite, wighmanite, wiluite, and wis minerals or compounds that generate the same in a copper erite, among others. electrodeposition process of claim 1 COMPRISING a com 9. Use of oxygenated or polyoxygenated weak acids, or pound that can be, among others, a phosphorus compound. minerals or compounds that generate the same in a copper 12. Use of oxygenated or polyoxygenated weak acids, or electrodeposition process of claim 1 COMPRISING the min minerals or compounds that generate the same in a copper eral phosphorus that can be selected, without limitation, from electrodeposition process of claim 10 COMPRISING a com aheylite, aldermanite, alforsite, alluaudite, althausite, pound that is a boron compound, selected preferably, without amblygonite, anapaite, apatite, arctite, ardealite, arupite, limitation, from borax, borates, and boranes, among others. augelite, autunite, babefphite, barbosalite, baricite, barringer ite, bassetite, bauxite, bearthite, belovite, benauite, beraunite, 13. Use of oxygenated or polyoxygenated weak acids, or berlinite, bermanite, bertossaite, beryllonite, beusite, biphos minerals or compounds that generate the same in a copper phamite, bobierrite, boggildite, bonshtedtite, brabantite, bra electrodeposition of claim 11 COMPRISING a compound dleyite, brazilianite, brianite, britholite, brushite, buch that is a phosphorous compound, preferably selected, without waldite, cacoxenite, canaphite, cassidyite, chalcosiderite, limitation, from phosphates, phosphonates, phosphoranes, cheralite, churchite, chlorapatite, coffinite, collinsite, coeru phosphides, sodium hypophosphite, phosphine oxide, phos leolactite, corkite, cornetite, crandallite, crawfordite, cureto phorus pentafluoride, phosphorus trichloride, hexafluoro nite, cyrilovite, diadochite, dittmarite, dorfmanite, dufrenite, phosphoric acid, and phosphorus (III) and (V) oxide, among dumontite, earlshannonite, ehrleite, eosphorite, fairfieldite, others. farringtonite, florencite, fluellite, fluorapatite, fluorellesta 14. Use of oxygenated or polyoxygenated weak acids, or dite, foggite, formacite, francoanellite, fransoletite, fron minerals or compounds that generate the same in a copper delite, furongite, gainesite, galileiite, gatehouseite, gatum electrodeposition process of claim 1 COMPRISING baite, giniite, girvasite, glucine, gorceixite, gordonite, improved current consumption efficiency and increased cop goyazite, graftonite, grattarolaite, grayite, hentschelite, herd per recovery from the electrolyte solution. erite, heterosite, hinsdalite, holtedahlite, hopeite, hotsonite, 15. A copper electrowinning procedure COMPRISING: hureaulite, hurlbutite, hydroxylapatite, hydroxylherderite, Addition of a necessary quantity of an oxygenated or poly hydroxyl-piromorphite, isokite, jagowerite, kaluginite, kidw oxygenated weak acid, or a compound or a mineral that ellite, kingite, kingsmountite, kintoreite, kleemanite, kolbec generate the same in said copper electrodeposition pro kite, koninckite, kosmarite, kovdorskite, kribergite, kryzha novskite, kuksite, lacroixite, landesite, laubmanite, laueite, CeSS lazulite, lehnerite, lermontovite, leucophosphite, libethenite, where the necessary quantity of weak acid will depend on likasite, lipscombite, liroconite, lithiophilite, lithiophospha the characteristics of the mineral, the electrolyte solu tite, lithiophosphate, lomonosovite, ludlamite, luneburgite, tion, and the current density used. magniotriplite, mahlmoodite, mangangordonite, maricite, 16. A copper electrowinning procedure of claim 14 COM matulaite, metaankoleite, metaswitzerite, metatorbenite, PRISING the addition of an oxygenated or polyoxygenated metavariscite, metavauxite, mimetite, mitridatite, monazite, weak acid, preferably, to said electrodeposition chamber. US 2016/0194771 A1 Jul. 7, 2016

17. A copper electrowinning procedure of claim 15 COM PRISING said weak acid, preferably, boric acid or phospho ric acid. 18. A copper electrowinning procedure of claim 14 COM PRISING said mineral added to said electrodeposition pro CèSS. 19. A copper electrowinning procedure of claim 17 COM PRISING said mineral, preferably, a boron or phosphorus mineral. 20. A copper electrowinning procedure of claim 17 COM PRISING said compound, preferably, a boron or phosphorus compound. 21. A copper electrowinning procedure of claim 17 COM PRISING said compound, preferably selected from borax, borates, and boranes, among others. 22. A copper electrowinning procedure of claim 17 COM PRISING said compound, preferably selected from borax. 23. A copper electrowinning procedure of claim 17 COM PRISING said compound, preferably selected from phos phates, phosphonates, phosphoranes, phosphites, phos phides, sodium hypophosphite, phosphine oxide, phosphorus pentafluoride, phosphorus trichloride, hexafluorophosphoric acid, and phosphorus (III) and (V) oxide, among others. 24. Use of oxygenated or polyoxygenated weak acids, or minerals or compounds that generate the same in copper electrowinning of claim 1 COMPRISING said acid having a dissociation constant that varies between 1.80×107* and 55.50.